JPH0152383B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel and useful method for producing fluoroalkyl surfactant compounds,
More specifically, the present invention relates to an improved production method in which the reaction is carried out by setting the hydrogen ion concentration of the reaction solution within a specific range at the reaction temperature. Surfactants having a fluoroalkyl group, in which the hydrogen atom of the alkyl group is replaced with a fluorine atom, usually provide a low-energy surface at low concentrations.
Furthermore, since such surfactants have the advantage of being chemically stable, they have begun to be used in various fields such as leveling agents for water-based paints and anti-fog mist agents. Among the major uses of such surfactants is water film-forming foam fire extinguishing agents, in which fluoroalkyl group-containing surfactant compounds extinguish fires by spreading a water film or bubbles on flammable liquids. It has the advantage of well preventing the danger of ignition again, and its suitability for such applications is attracting particular attention. By the way, fluoroalkyl group-containing surface-active compounds suitable for use in such water-forming foam fire extinguishing agents include:
Not only does it significantly lower the surface tension of water, it also foams well and has a long foam return time.
It must dissolve well even in hard water such as seawater.
Previous research has shown that active compounds suitable for such uses have a general formula in which a fluoroalkyl group and a hydrophilic group are bonded via an amine group. [R _f in the formula represents a fluoroalkyl group having 4 to 18 carbon atoms, in which the hydrogen atom on the carbon atom is substituted with a fluorine atom, and A represents the general formula (However, R ₂ in the formula represents a hydrogen atom or an alkyl group having 3 or less carbon atoms.) Q is an alkylene group having 4 or less carbon atoms, and R ₁ is an alkylene group having 6 carbon atoms. The following alkyl group or hydroxy-substituted alkyl group, Z is

【formula】

【formula】

【formula】 [However, X in the formula represents a halogen atom, and Q and Z are as described above. ]

It can be obtained by dehydrohalogenation using an alkyl halide represented by: However, the above method (1) itself
Although the reaction conditions are mild and are very convenient for synthesis, the above-mentioned cyclic compounds generally carry the risk of toxicity; for example,
Since propane sultone has been shown to be carcinogenic, the use of cyclic compounds is considered to be a fatal flaw in producing the above-mentioned surfactant compounds by this type of reaction. I can say that. On the other hand, in method (2) above, the alkyl halide as a raw material and the reaction product are reacted in water or alcohol as a good solvent, but this alkyl halide itself is not compatible with the target amine compound. This reaction is extremely complex, as it not only reacts with the OH groups in this solution, but also produces hydroxyalkyl and alkyl ether as by-products. However, the present inventors sought a method for producing a fluoroalkyl surface-active compound that does not involve any of these inconveniences, and as a result of intensive studies on the above-mentioned reaction format (2), the present invention was completed. That is, the present invention provides an interface as represented by the general formula [] by reacting a perfluoroalkylamine represented by the general formula [] shown above with an alkyl halide represented by the general formula [] shown above. The present invention provides a new and useful method for producing active compounds, which comprises using water as a solvent and adjusting the hydrogen ion concentration of the reaction solution to 9 to 12 at the reaction temperature. Here, specific examples of the perfluoroalkylamine represented by the above-mentioned general formula [] are as follows. C ₆ F ₁₃ SO ₂ NHCH ₂ CH ₂ CH ₂ NH ₂ (-1) _{C 6} F ₁₃ SO ₂ NHCH ₂ CH 2 CH ₂ N(CH ₃ )H (-2) C ₆ F ₁₃ SO ₂ N(CH ₃ )CH ₂ CH ₂ CH ₂ N(CH ₃ )H (−3) C ₆ F ₁₃ SO ₂ N(CH ₃ )CH ₂ CH ₂ CH ₂ N(CH ₂ CH ₂ OH)H(−
4) C ₆ F ₁₃ SO ₂ NHCH ₂ CH ₂ NH ₂ (−5) C ₆ F ₁₃ SO ₂ NHCH ₂ CH ₂ N(CH ₃ )H (−6) C ₈ F ₁₇ SO ₂ NHCH ₂ CH ₂ CH ₂ NH ₂ (-7) C ₈ F ₁₇ SO ₂ NHCH ₂ CH ₂ CH ₂ N (C ₂ H ₅ ) H (-8) C ₇ F ₁₅ CONHCH ₂ CH ₂ CH ₂ NH ₂ (-9) C ₇ F ₁₅ CONHCH ₂ CH ₂ CH ₂ N(CH ₃ )H (−10) C _o F _2o+1 CONHCH ₂ CH ₂ CH ₂ N(CH ₃ )H (however, n is 6 to
12 integers) (-11) C ₆ F ₁₃ CH ₂ CH ₂ CONHCH ₂ CH ₂ CH ₂ N(CH ₃ )H (-12) C ₆ F ₁₃ CH ₂ CH ₂ CON(CH ₃ ) CH ₂ CH ₂ CH ₂ NH ₂ (−13) or C ₆ F ₁₃ CH ₂ CH ₂ CH ₂ CON(CH ₃ ) CH ₂ CH ₂ N(CH ₂ CH ₂ OH)H
(-14) Specific examples of the alkyl halide represented by the above general formula [] include sodium 3-chloropropanesulfonate, potassium 3-chloropropanesulfonate, sodium 2-bromoethanesulfonate, -bromoethanesulfonic acid, 3-
Sodium chlorpropanecarboxylate, ammonium 3-chloropropanecarboxylate, 4-chlorobutanol, sodium 2-chloroethane monophosphate,
Ethylene chlorohydrin or Cl− (CH ₂ CH ₂ O−)
₃ CH ₂ CH ₂ OH, etc. Furthermore, water is necessary as the reaction solvent used in carrying out the method of the present invention. At this time, in addition to this water, a water-soluble organic solvent may be added for the purpose of dissolving the reaction products and the above-mentioned raw materials, or for the purpose of increasing the reaction temperature. Such organic solvents include methanol, ethanol, isopropyl alcohol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, dioxane, tetrahydrofuran, pyridine, acetone or methyl ethyl ketone. Although they are representative, ethylene glycol monoethyl ether and diethylene glycol monobutyl ether are particularly preferable, considering that they do not react with the amine compound, that is, are inert, and have a boiling point. When such an organic solvent is used in combination, any mixing ratio of the organic solvent and water may be used as long as the reaction proceeds well and the hydrogen ion concentration can be measured reliably. Further, the reaction temperature in carrying out the method of the present invention may be any temperature as long as the desired N-alkylation reaction proceeds well, but it is usually preferably in the range of 40 to 100°C. . Furthermore, the hydrogen ion concentration mentioned above is expressed in PH, but since it depends on the temperature, reaction solvent composition, or concentration of raw materials or reaction products, it refers to the value under these reaction conditions, especially the reaction temperature. . this
If the pH is less than 9, the basicity as a catalyst in the dehydrohalogenation reaction will be insufficient and the N-alkylation reaction will be slow;
When the number exceeds 12, the raw material compound itself, which is the alkyl halide, reacts with the hydroxyl group in the reaction solvent such as water or alcohol (side reaction).
Both are disadvantageous because they tend to proceed faster than the desired N-alkylation reaction. The molar ratio of the alkyl halide to the fluoroalkylamine is suitably in the range of 0.8 to 2.4. If it is less than 0.8, the yield of the desired fluoroalkyl-containing surfactant compound will be low, which is disadvantageous.On the other hand, if it exceeds 2.4, in addition to the target compound represented by the above general formula [], 1 mol of it will be added. General formula of alkyl halide added form [However, R _f , A, Q, X, R ₁ and Z in the formula are all as described above. ] This is disadvantageous because the amount of quaternized cationic compounds produced increases. The perfluoroalkyl group-containing surfactant compound represented by the above general formula [] obtained by the method of the present invention may be used alone or as a mixture with a quaternized cationic compound represented by the above general formula []. By mixing it with other fluoric carbide or hydrocarbon surfactants, it can be used as a water film-forming fire extinguishing foam or as a reinforcing agent for protein foam fire extinguishing agents. Next, the present invention will be specifically explained with reference to Examples and Comparative Examples. Unless otherwise specified, "%" means
All values are expressed as "% by weight". Example 1 Into a 24-necked flask equipped with a thermometer, a dropping funnel with a condenser, and a stirring bar, 70.0 g (0.149 mol) of the compound (-1) listed above, 3-
Sodium chlorpropanesulfonate 32.2g (0.179
mol), 310 g of water and 420 g of diethylene glycol monobutyl ether, and in the remaining one mouth,
Set the one-legged PH meter electrode, start heating and stirring, and increase the temperature by 10% until the PH meter shows 9.0 to 9.5.
Adjust by dropping aqueous caustic soda solution. Keep the reaction temperature constant at 95°C. By doing so, the PH completely stops changing after about 4 hours. Thus, the reaction was completed by heating and stirring for a total of 7 hours, but gas chromatography analysis of the reaction solution revealed that the conversion rate of the raw material (-1) was 95.8%, and a thin layer was formed. From the results of chromatographic analysis, the majority of It was also confirmed that Examples 2 and 3 and Comparative Examples 1 to 3 Surface-active compounds were obtained in the same manner as in Example 1, except that the PH range was changed as shown in Table 1. The conversion rate by PH is shown in the same table.

[Table] Example 4 Into a 24-necked flask equipped with a thermometer, a dropping funnel with a condenser, and a stirring bar, 70.0 g (0.149 mol) of the compound (-1) listed above and 3-
Sodium chlorpropanesulfonate 32.3g (0.179
mol) and 730 g of water were added, and a one-legged PH meter electrode was set in the remaining opening. Start heating and stirring, and adjust by dropping 10% caustic Soda aqueous solution so that the pH meter shows 9.0 to 9.5. Keep the reaction temperature constant at 95°C. By doing this, the PH completely stops changing after about 4 hours. Thus, the reaction was completed by heating and stirring for a total of 7 hours, but gas chromatography analysis of the reaction solution revealed that the conversion rate of the raw material (-1) was as shown in Table 2. 90.0
%, and from the results of thin layer chromatography analysis, most of the It was also confirmed that Examples 5 and 6 and Comparative Examples 4 to 6 Surface-active compounds were obtained in the same manner as in Example 4, except that the PH range was changed as shown in Table 2. The conversion rate by PH is shown in the same table.

[Table] In this way, the selection of the PH range is important in converting the raw material (-1) to obtain the target product, and PH9.0
It was found that ~12.0 is preferable.

Claims (1)

[Claims] 1. General formula [R _f in the formula represents a fluoroalkyl group having 4 to 18 carbon atoms, in which the hydrogen atom on the carbon atom is substituted with a fluorine atom, and A represents the general formula (However, R ₂ in the formula represents a hydrogen atom or an alkyl group having 3 or less carbon atoms.) Q is an alkylene group having 4 or less carbon atoms, and R ₁ is an alkylene group having 6 carbon atoms. It represents the following alkyl group or hydroxy-substituted alkyl group. ] A fluoroalkylamine represented by the general formula [Formula] [Formula] -OH or -(OCH ₂ CH ₂ -) _o OH (However, M in the formula represents a hydrogen atom, an alkali metal, or an alkylamine having 6 or less carbon atoms, and n is an integer from 1 to 5. ) represents a functional group represented by ] by reacting with an alkyl halide represented by the general formula [However, R _f , A, Q, R ₁ and Z in the formula are as described above. ] A fluoroalkyl surface-active compound characterized in that the hydrogen ion concentration of the reaction solution is adjusted to a range of 9 to 12 at the reaction temperature using water as a solvent in order to obtain the surface-active content shown in Manufacturing method.