JPH0259131B2 - - Google Patents

Description

[Detailed description of the invention]

Industrial Application The present invention relates to novel surfactants containing simultaneously perfluorinated chains (R _F ) and hydrogenated chains (R _H ), which are used in particular as surfactants or as intermediates for the synthesis of surfactants. It is related to chemical compounds. Prior Art Fluorinated surfactants have the property of greatly reducing the surface tension of aqueous solutions and are therefore useful in the preparation of mixtures of fire extinguishing agents, especially hydrocarbon extinguishing agents, for extinguishing fires. extremely important. In this fire extinguisher composition, a fluorinated surfactant is generally used in combination with a non-fluorinated surfactant to quickly form a fire-resistant and durable film on the surface of the water-insoluble hydrocarbon. used in combination with agents. PROBLEM SOLVED BY THE INVENTION Although beneficial results can be obtained by using mixtures of fluorinated and non-fluorinated surfactants, the formulation of digestive compositions For example, there is a need for a single surfactant that simultaneously contains perfluorinated and hydrogenated chains. From this point of view, it is an object of the present invention to provide compounds comprising perfluorinated and hydrogenated chains. Means for solving the problem The compounds according to the invention are represented by the following general formula: (In the above formula, R _F represents a linear or branched perfluoroalkyl group containing 1 to 20 carbon atoms, R _H represents a linear or branched alkyl group containing 1 to 18 carbon atoms, m is 0 to 2
, X is an OH group or a NR ₁ R ₂ group, and R ₁ and R ₂ may be the same or different,
each is a hydrogen atom or a methyl group). Particularly preferred are compounds in which the R _F and R _H groups contain 4 to 12 carbon atoms and the nitrogen is unsubstituted (R ₁ =R ₂ =H). The invention furthermore relates to mixtures of two compounds of this type, one of which is represented by the formula: The other compound is represented by the following formula: (In the above formula, m' is 1 or 2,
n is an integer from 1 to 17, and the molar ratio of -a/-b ranges from 0.1 to 10). Compounds according to the invention in which X is a group NR ₁ R ₂ are
In the presence of excess formamide or a methylated derivative of formamide, the following general formula: R _F -(CH ₂ ) _P -CH=CH-C _o H _2o+1 () (in the above formula, P is 0 or 1,
(n is an integer from 1 to 17) It can be synthesized by photoamidation of a polyfluorinated olefin represented by: This reaction is preferably carried out by irradiating a mixture containing the polyfluorinated olefin () and formamide or a methylated derivative thereof with ultraviolet light in the presence of acetone as an initiator. This operation consists of 2-methyl-1-propanol,
Preferably it is carried out in a homogeneous medium consisting of a solution of the reactants (olefin, formacide and acetone) in an inert organic solvent such as 1,4-dioxane, preferably tert-butanol. Except in the case of dimethylformamide, microemulsions of the reactants obtained using nonionic surfactants and other surfactants of the alcohol type may be irradiated with ultraviolet radiation. One of the two surfactants mentioned above contains fluorine and the other is fluorine-free. Nonionic surfactants that can be used include, among others, ethoxylated alkylphenols, polycondensates of ethylene oxide and propylene (Pluronics);
and ethoxylated polyfluoroalcohols. Examples of other surfactants mentioned above include aliphatic alcohols such as hexanol, heptanol and octanol, R _F such as 2-perfluorobutylethanol and its perfluorohexyl and perfluoroctyl analogs.
Mention may be made of fluoroaliphatic alcohols of the C ₂ H ₄ OH type. In order to obtain suitable microemulsions, it is necessary to use amounts of nonionic surfactants and other surfactants mentioned above whose weight ratio ranges from 0.5 to 1.5, preferably approximately equal to 1. It is. From this point of view, a polycondensate of nonylphenol and 5 to 14 moles of ethylene oxide and a 2-
combination with butylperfluoroethanol and from 10 with 2-hexylperfluoroethanol
A combination of 15 mol of a polycondensate of ethylene oxide with 1-hexanol, 1-heptanol or 1-octanol is particularly suitable. The irradiation is preferably carried out at a temperature of 25 to 50°C, and the irradiation time can vary within a wide range depending on the intensity of the irradiation and is usually between 12 and 60 hours. The best yield is obtained when the irradiation time is 30 to 50 hours. As before, the operation is carried out in the presence of excess formamide or its methylated derivative. The formamide (or methylated derivative)/olefin () molar ratio can vary within a wide range, but is generally from 10 to 120, more preferably from 40 to Make it in the 90 range. The amount of acetone used as initiator can vary within a wide range, but the acetone/formamide molar ratio is between 0.03 and 0.2, preferably between 0.05 and 0.05.
Preferably, this amount is determined to be in the range 0.09. Regardless of the method chosen (homogeneous media or microemulsion), photoamidation of an olefin of the formula produces a mixture of two amides: (However, the symbols m', n, R _F , R ₁ and R ₂ have the same meanings as above). However, when the operation is carried out in a homogeneous medium, the corresponding -a amide is usually obtained, in which the carbamoyl group is fixed to the olefin carbon furthest from the perfluoro chain. In the case of microemulsions, the major product is often the corresponding -b amide in which the olefin carbon closest to the perfluoro chain is amidated. Amide-a
When it is necessary to separate and -b, fluorinated solvents (e.g. trichlorotrifluoroethane)
can be separated by conventional methods such as extraction or pre-chromatography. The starting material polyfluoroolefin () is
It is a known substance. When P is 0 in the above formula, that is, the olefin R _F -CH=CH-C _o H _2o+1 is
Usually, perfluoroalkyl iodide R _F I is added to olefin C _o H ₂₊₁ CH=CH ₂ (G.V.
Day. GVDTIERS, "Journal of Organic Mistry" 27, 2261,
1962 and N. Oh. Brace (NO
BRACE), Journal of Organic Chemistry
37, 2429, 1972),
Next generated iodohydrin R _F CH ₂ CHI―C _o
H _2o+1 can be obtained by dehydriodination with potassium hydroxide purified from alcohol. Also, when P is 1, that is, olefin R _F
The polyfluoroolefin in the case of CH ₂ -CH=CH-C _o H _2o+1 is obtained by reacting -2-ethylperfluoroalkyltrifosnium iodide with an aliphatic aldehyde. This 2-ethylperfluoroalkyltriphosphonium iodide itself is
- Obtained by reacting ethylpeterfluoroalkyl with triphenylphosphine (B.ESCOULA and others, "Synthetic Chemistry (Syn-
15(1), 35, 1985 and C.
C. CECUTTI and others ``Journal of Dispersion Science
7(3), 307, 1986). Compounds of the invention in which X is an OH group can be prepared by hydrolysis of amides. This hydrolysis can be carried out in an aqueous medium using a base. This base is preferably sodium hydroxide, but may also be potassium hydroxide. This operation is carried out in a strongly basic medium of 12 to 36N, preferably 20 to 30N, at 100 to 160°C, preferably from 120 to
Carry out at a temperature of 140°C. Hydrolysis is believed to be complete after 24 hours. After acidifying the reaction mixture, the acid produced can be separated by conventional methods, in particular extraction using a solvent selected from among chlorofluorinated hydrocarbons, such as, for example, trichloro-trifluoro-ethane. can. The acids according to the invention are oily or solid. This acid can be easily converted into a water soluble salt by conventional methods. For example, it can be converted into a potassium salt by the action of an ethanolic potassium solution. The polyfluorinated acids and their salts according to the invention can be used as surfactants or as amides as intermediates in the synthesis of surfactants and the like. The following examples illustrate the invention but do not limit it in any way. The NMR ¹⁹ _F spectrum designation indicates trifluoroacetic acid. Example 1 Production of 1,1,1,2,2,3,3,4,4-nonafluoropentadecane-6 and 7-carboxylamide Fluorinated olefin C ₄ F ₉ - in a Pyrex tube
CH ₂ -CH=CH-C ₈ H ₁₇ , 0.744 g, formamide 5.88 ml, tert-butanol 15.84 ml and acetone
Introduce 0.83ml. Next, a stream of argon is applied for 5 minutes to remove oxygen from the air. The above tube was then attached to a rotating forest structure inside a tubular jacket surrounded by 16 UV lamps (input = 300 nm, P = 16 W) kept at a temperature of approximately 30 to 35°C, and exposed to UV light for 2 days. Expose to light. The oxyamide precipitate formed during the synthesis is then removed by filtration, the filtrate is evaporated under vacuum (2000 Pa) and the residue is recovered with 5 ml of water. It is purified by recrystallization in a mixture of equal volumes of acetone and petroleum ether and dried over (666 Pa) P ₂ O ₅ in an oven. 0.57 g of a solid melting at 80° C. is thus obtained. This solid was analyzed (NMR ¹ H,
By NMR ¹⁹ F and PVC) it is found to be an isomer of the following formula: However, the a/b ratio is 2.89. Example 2 1, 1, 1, 2, 2, 3, 3, 4, 4, 5,
5,6,6-tridecafluorotridecane-8
and production of 9-carboxylamide Fluorinated olefin C ₆ F ₁₃ -CH ₂ -CH=CH-
The procedure is as in Example 1, except that 0.832 g of C ₄ H ₉ is used. 0.58 g of a solid is obtained which melts at 78°C. When this is analyzed by NMR and PVC, it is found that it is an isomer pair of the following formula: The a/b ratio is 1.39. Example 3 1, 1, 1, 2, 2, 3, 3, 4, 4, 5,
Production of 5,6,6,7,7,8,8-heptadecafluoro-pentadecane-10 and 11-carboxylamide Fluorinated olefin C ₈ F ₁₇ —CH ₂ —CH=CH—
Working as in Example 1 using 1.032 g of C ₄ H ₉ as starting material, 0.98 g of a solid melting at 88° C. is obtained.
It is found by NMR and PVC analysis to be an isomer of the following formula: However, the a/b ratio is 1.22. Example 4 1, 1, 1, 2, 2, 3, 3, 4, 4, 5,
Production of 5,6,6,7,7,8,8-heptadecafluoro-eicosane-9 and 10-carboximylamide Fluorinated olefin G ₈ F ₁₇ -CH=CH-
Using 1.2 g of C ₁₀ H ₂₁ as a starting material and carrying out the same procedure as in Example 1, 0.82 g of a solid having a melting point of 92° C. is obtained. It is an isomer of the following formula: However, the a/b ratio is 7.71. Example 5 Preparation of 1,1,1,2,2,3,3,4,4-nonafluoro-pentadecane-6 and 7-carboxymyl acid A Pyrex tube is introduced with a microemulsion prepared from the following materials: : -Fluorinated olefin C ₄ F ₉ -CH ₂ -CH=CH-
C ₈ H ₁₇ 0.26g -Formamide 1.48g -2-Perfluorobutylethanol 1.63g -Polyethoxylnonylphenol (10.5 mol of ethylene oxide per 1 mol of nonylphenol) 1.63g -Acetone 0.18ml Degassed with argon as in Example 1 However, when the microemulsion was injected into the CPV after 2 days of irradiation, it was found that the following isomers were present. However, the ratio of a/b is equal to 0.95. Example 6 1, 1, 1, 2, 2, 3, 3, 4, 4, 5,
Preparation of 5,6,6,7,7,8,8-heptadecafluoro-eicosane-9 and 10-carboxylamide Amides of: To prepare the fluorinated olefin C ₈ F ₁₇ −
Example 5 is carried out using 0.26 g of CH=CH-C ₁₀ H ₂₁ and 1.63 g of four polyethoxylated nonylphenols with different numbers of ethylene oxides (EON). The results obtained are shown in the table below:

[Table] Same fluorinated olefin C ₈ F ₁₇ −CH=CH−
Another series of experiments was carried out using C ₁₀ H ₂₁ fluorinated nonionic surfactants containing the same amount (1.63 g) of the above polyethoxylated nonylphenol C ₆ F ₁₃ C ₂ H ₄ (OC ₂ H ₄ ) ₁₂ -OH and the same amount (1.63 g) of the above 2-perfluorobutylethanol (1-hexanol, 1-heptanol, and 1-octanol)
Replaced with The results obtained are shown in the table below:

[Table] Example 7 1, 1, 1, 2, 2, 3, 3, 4, 4, 5,
Preparation of 5,6,6,7,7,8,8-heptadecafluoro-eicosane-N-methyl-9 and 10 carboxylamide Fluorinated olefin C ₈ F ₁₇ -CH=CH-
Proceeding as in Example 1 using 1.2 g of C ₁₀ H ₂₁ and 8.65 ml of N-methylformamide as starting materials, 1.1 g of a paste is obtained which melts at temperatures below 50°C. It is an isomer of: However, the a/b ratio is 1.08. Example 8 1, 1, 1, 2, 2, 3, 3, 4, 4, 5,
Preparation of 5,6,6,7,7,8,8-heptadecafluoroeicosane-N-methyl-9 and 10 carboxylamide A microemulsion prepared from the following starting materials is introduced into a Pyrex tube: -Futsu Hydrogenated olefin C ₈ F ₁₇ −CH=CH−C ₁₀ H ₂₁
0.26g -N-Methylformamide 1.48g -2-Perfluorobutylethanol 1.63g -Polyethoxylated nonylphenol (12 moles of ethylene oxide per mole of nonylphenol)
1.63g - Acetone 0.18ml After degassing with argon in the same manner as in Example 1 and irradiating for 2 days, the microemulsion was injected and the following isomers were found to be present. However, the a/b ratio is 0.55. Example 9 1, 1, 1, 2, 2, 3, 3, 4, 4, 5,
5,6,6,7,7,8,8-heptadecafluoroeicosan-N,N-dimethyl-9 and
Production of 10-carboxylamide Fluorinated olefin C ₈ F ₁₇ −CH=CH−
When working in the same manner as in Example 1 using 1.2 g of C ₁₀ H ₂₁ and N,N-dimethylformamide as starting materials,
1.11g of oil is obtained. It is an isomer of the following formula: However, the a/b ratio is 1.01. Olefins used in Examples 4 and 6 to 9
_C8F17 - _CH =CH- _C10H21 was produced by the following procedure _. Perfluorooctyl iodide 546g
and 5 g of azobisisobutyronitrile are placed in a reactor equipped with a stirrer, a reflux condenser, and an outflow flask. This mixture was heated to 75°C, then 1
- Introduce 261 g of dodecene over 1 hour. After 6 hours of reaction, 2.5 g of azobisisobutyronitrile
and heated to 75°C over 4 hours. Subsequently, the reaction mixture is distilled to remove excess perfluorooctyl iodide and dodecene (110-160 °C under 2666 Pa). Next, a solution of 68 g of potassium hydroxide in 250 ml of ethanol is added to 678 g of the reaction product, keeping the temperature at 40-45°C.
After adding 1 part of water and decanting, the organic phase (563 g)
is separated and distilled in vacuo (120°C/133Pa) to purify the obtained olefin. Example 10 Preparation of 1,1,1,2,2,3,3,4,4-nonafluoropentadecane-6 and 7-carboxylic acid In a flask equipped with a reflux condenser, the solid obtained in Example 1 A paste mixture of 125 mg, 2 ml of water, and 2 g of sodium hydroxide was heated to 130 mg over 24 hours.
Heat to ℃. After cooling this reaction mixture, 37
Add 4.2 ml of % hydrochloric acid to bring the pH to 1 and keep stirring for 3 hours. Extraction of the aqueous phase with 1,1,2-trichloro-1,2,2-trifluoroethane and evaporation of the solvent gives 52 mg of a yellow oil. Analysis reveals that this is an acid with the following formula: Infrared absorption spectrum: 2960 (free OH group); 1711 (C=O) 1460 (CHαCO ₂ H): 1236 (CF) NMR ¹ H spectrum (CD ₃ COCD ₃ ): 0.77 (3p, m, CH ₃ ) 1.16 (14p, m, CH ₂ ) 2.14 (1p, m, CH) 3.25 (4p, m, CH ₂ α and βCF ₂ ) NMR ¹⁹ F spectrum (CD ₃ COCD ₃ ): -5.59 (3f, m, CF ₃ ) -38.83 (2f, m, CF ₂ αCH ₂ ) -48.61 (2f, m, CF ₂ βCH ₂ ) -50.36 (2f, m, CF ₂ αCF ₃ ) Example 11 1, 1, 1, 2, 2, 3, 3, 4, 4, 5,
5,6,6-tridecafluorotridecane-8
Preparation of 9-carboxylic acid Using 138 mg of the solid obtained in Example 2 and proceeding as in Example 10, 100 mg of a yellow oil consisting of the following acids are recovered: Infrared absorption spectrum: 2969 (free OH group): 1714 (C=O) 1450 (HαCO ₂ H): 1208 (CF) Example 12 1, 1, 1, 2, 2, 3, 3, 4, 4 ,5,
Production of 5,6,6,7,7,8,8-heptadecafluoro-eicosane-9 and 10-carboxylic acid When the same operation as in Example 10 was carried out using 189 mg of the solid of Example 4, the following was obtained. 63 mg of yellow oil composed of acid is obtained: Infrared absorption spectrum: 2960 (OH free radical); 1720 (C=O) 1470 (CHαCO ₂ H); 1200 (CF) NMR ¹ H spectrum (CD ₃ COCD ₃ ): 0.92 (3p, m, CH ₃ ) 1.30 (18p, m, CH ₂ ) 2 (1p, m, CH) 2.87 (2p, m, CH ₂ αCF ₂ ) NMR ¹⁹ F spectrum (CD ₃ COCD ₃ ): -5.27 (3f, m, CF ₃ ) - 37.34 (2f, m, CF ₂ αCH ₂ ) -46.06 (6f, m, CF ₂ ) -46.69 (2f, m, CF ₂ γCF ₃ ) -47.75 (2f, m, CF ₂ βCF ₃ ) -50.35 (2f, m, CF ₂ αCF ₃ )

Claims (1)

[Claims] 1. Compounds represented by the following formulas (-a) and (-b) with a molar ratio of (-a)/(-b)
Mixtures containing in proportions from 0.1 to 10: (where R _F is a linear or branched polyfluoroalkyl group containing from 4 to 12 carbon atoms,
m' is 1 or 2, n is an integer from 4 to 11, and X is an OH group or a NR ₁ R ₂ group; in the latter case, R ₁ and R ₂ are each a hydrogen atom or a methyl group; (and may be the same or different from each other). 2. The mixture according to claim 1, wherein R ₁ and R ₂ are hydrogen atoms. 3 The following general formula (): R _F - (CH ₂ ) _P - CH = CH - C _o H _2o+1 () (where R _F is a linear or branched polyester containing 4 to 12 carbon atoms. is a fluoroalkyl group,
p is 0 or 1 and n is an integer from 4 to 11) in the presence of an excess of formamide or its methyl derivative. Formulas (-a) and (-b): (where R _F is a linear or branched polyfluoroalkyl group containing from 4 to 12 carbon atoms,
m' is 1 or 2, n is an integer from 4 to 11, and X is an OH group or a NR ₁ R ₂ group; in the latter case, R ₁ and R ₂ are each a hydrogen atom or a methyl group; (which may be the same or different) in a molar ratio of (-a)/(-b) from 0.1 to 10. 4. The method according to claim 3, characterized in that the mixture of polyfluorinated olefin () and formamide or its methyl derivative is irradiated with ultraviolet light in the presence of acetone as an initiator. 5 Polyfluorinated olefin () and
5. Process according to claim 4, characterized in that it is operated in a homogeneous solution of formamide and acetone in an inert organic solvent. 6. The method according to claim 5, characterized in that the solvent is tert-butanol. 7 Polyfluorinated olefin () obtained using a nonionic surfactant and an alcoholic surfactant, one containing fluorine and the other not containing fluorine, formamide, and acetone. 7. The method according to claim 6, characterized in that the microemulsion is irradiated with ultraviolet light. 8. The nonionic surfactant is selected from the group consisting of ethoxylated alkylphenols, polycondensates of ethylene oxide and propylene, and ethoxylated polyfluoroalcohols. Claim No. 7
The method described in section. 9. The method according to claim 7 or 8, wherein the alcoholic surfactant is an aliphatic alcohol or a fluorinated aliphatic alcohol. 10 Claim No. 1, characterized in that the nonionic surfactant is a polycondensate of nonylphenol and 5 to 14 moles of ethylene oxide, and the alcoholic surfactant is 2-butyl perfluoroethanol. The method described in Section 7. 11 The nonionic surfactant is a polycondensate of 2-perfluorohexylethanol and 10 to 15 moles of ethylene oxide, and the alcoholic surfactants are hexanol-1 and heptanol-1.
or Octanol-1, the method according to claim 7. 12. Process according to any one of claims 3 to 11, characterized in that the molar ratio of formamide/polyfluorinated olefin () is from 10 to 120. 13. Process according to any one of claims 3 to 12, characterized in that the acetone/formamide molar ratio is from 0.03 to 0.2.