JPH0118907B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula [] (However, in the formula, Rf is a perfluoroalkyl group containing 1 to 20 carbon atoms, Z is -SO ₂ - or -CO-, and R, R' and R'' are a hydrogen atom or a lower alkyl group. ) In this specification, the perfluoroalkyl group refers to not only linear and branched groups but also cyclic groups (e.g. perfluorocyclohexyl) or a combination thereof. It is defined as including those with a structure in which an oxygen atom is interposed in the carbon atom chain (for example, (CF ₃ ) ₂ CFOCF ₂ CF ₂ --). Some fluorine-containing diepoxy compounds are, for example, Ind.Eng.Chem.Prod.Res.Dev.Vol.17, No.1
(1978), p. 8 and 10, and is well known. It is a general formula (In the formula, Rf represents a perfluoroalkyl group)
These compounds are clearly distinguishable from the compounds of the present invention represented by the general formula []. An object of the present invention is to provide a novel fluorine-containing diepoxy compound that differs in properties from the above-mentioned known fluorine-containing diepoxy compounds in various respects. As a result of intensive and detailed research into the reaction of perfluoroalkyl group-containing amide and sulfamide compounds with epihalohydrin compounds, the present inventors found that in the presence of a certain type of catalyst, epihalohydrin compounds react with perfluoroalkyl group-containing amides and sulfamide compounds and epihalohydrin compounds. We have discovered that fluorine-containing dihalohydrin compounds can be produced in high yield by selective ring-opening addition to the nitrogen atom of the amide group of sulfamide compounds.
Furthermore, this fluorine-containing dihalohydrin compound is
It has been discovered that a fluorine-containing diepoxy compound represented by the general formula [] can be converted to a fluorine-containing diepoxy compound represented by the general formula [] in high yield by reacting with an alkali compound, and
We have completed a method for producing fluorine-containing diepoxy compounds using short reaction times and simple operations. That is, the present invention has the general formula (): (wherein, Rf is a perfluoroalkyl group containing 1 to 20 carbon atoms, Z is -SO ₂ - or -CO-, and R, R' and R'' are hydrogen atoms to lower alkyl The present invention provides a fluorine-containing diepoxy compound represented by the following general formula []: Rf-Z-NH ₂ (wherein, Rf and Z have the above-mentioned meanings.) To the perfluoroalkyl group-containing compound represented by the general formula []:

[Formula] (In the formula, R, R′ and R″ have the above-mentioned meanings,
X is Cl, Br or I. ) By reacting the epoxy compound represented by the general formula [] by itself or in a solvent in the presence of a catalyst substance: (In the formula, Rf, Z, R, R', R'' and X have the above-mentioned meanings.) After obtaining the compound represented by the general formula []
It can be produced, for example, by reacting a compound with an alkali compound. The perfluoroalkyl group-containing compound represented by the general formula () used as a starting material in the present invention is well known and can be obtained commercially, or can be produced by a known method. Specific examples of these compounds are as follows. C ₈ F ₁₇ SO ₂ NH ₂ C ₆ F ₁₃ SO ₂ NH ₂ C ₁₀ F ₂₁ CONH ₂ C ₇ F ₁₅ CONNH ₂ C ₄ F ₉ SO ₂ NH ₂ C ₃ F ₇ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) CF ₂ CONH ₂ CF ₃ CF ₂ CF ₂ [OCF (CF ₃ )・CF ₂ ] ₄ OCF (CF ₃ )
CONH ₂ Epoxy compounds of the general formula () are also well known and are either commercially available or can be prepared by known methods. Specific examples of the epoxy compound represented by the general formula () are as follows. The reaction for obtaining a fluorine-containing diepoxy compound of general formula () from a perfluoroalkyl group-containing compound of general formula () is as follows: 1.
A reaction for forming a fluorine-containing dihalohydrin compound of general formula () by ring-opening addition of an epoxy compound, 2. This is a two-step reaction consisting of a reaction for producing a fluorine-containing diepoxy compound of formula (). The reaction 1) is carried out using the perfluoroalkyl group-containing compound of general formula () and the epoxy compound of general formula () in a molar ratio of 1:2 to 1:10, in the presence of a catalyst substance, either by itself or in a solvent. , temperature 20~
It is carried out at 150°C, preferably 50-120°C for 0.5-6 hours. The fluorine-containing dihalohydrin compound of the general formula () used in the reaction of 2) may be purified and isolated after the reaction of 1), but it is usually left in the reaction system after the reaction of 1) is completed. It is convenient to use. The reaction 2) is usually carried out in the solvent used in the reaction 1) at a temperature of 20 to 150°C, preferably 50 to 120°C,
This can be easily carried out by dropping a liquid alkaline substance such as a methanol solution of sodium methoxide or alcoholic potassium hydroxide until the liquid in the reaction system begins to exhibit acid-alkalinity. If excess alkali is added at this time,
It is undesirable that the ring-opening reaction of the produced fluorine-containing diepoxy compound occurs. The amount of the catalyst substance used in the reaction 1) is 1 to 30 mol%, preferably 5 to 20 mol%, based on the perfluoroalkyl group-containing compound of general formula (). Examples of compounds used as catalysts in the reaction 1) include the following. That is, the general formula: MAn (wherein M is an alkali metal or alkaline earth metal atom, A is Cl, Br or I,
n is 1 or 2) Lithium chloride, sodium chloride, potassium chloride, calcium chloride, magnesium chloride,
barium chloride, lithium bromide, sodium bromide,
These are potassium bromide, sodium iodide, and potassium iodide. Also effective are sodium carbonate, potassium carbonate, sodium acetate, and the like. Also, the general formula:

[Formula] (In the formula, R ¹ , R ² , R ³ and R ⁴ are linear or branched alkyl or alkenyl groups having 1 to 24 carbon atoms, and may contain an alicyclic or aromatic ring. , or R ¹ , R ² , R ³ may form a pyridine ring together with N, and Y is Cl, Br,
I, OH group, HSO ₄ group or p-CH ₃ C ₆ H ₄ SO ₃ group. ) Tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium hydroxide, tetramethylammonium hydrogen sulfate, tetramethylammonium p-toluenesulfonate,
Tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, trimethylcetylammonium bromide, trimethylbenzylammonium chloride, N-methylpyridinium bromide, N-methylpyridinium iodide, N-ethylpyridinium bromide, N-ethylpyridinium iodide, etc. It is valid. Of course, the present invention is not limited to these specific examples. Further, examples of the solvent to be used include, but are not limited to, the following. It goes without saying that the solvent should be selected in consideration of the solubility of the catalyst substance used in the reaction. Among these, compounds having a polyoxyethylene chain in the molecule are particularly suitable solvents. ethylene glycol, diethylene glycol,
Polyethylene glycol (average molecular weight 200 or more)
1000), methyl cellosolve, ethyl cellosolve,
Butyl cellosolve, methyl carbitol, ethyl carbitol, butyl carbitol, diglyme, polyethylene glycol monomethyl ether (average molecular weight 200 to 10,000), polyethylene glycol dimethyl ether (average molecular weight 200 to 10,000)
10000), methyl alcohol, ethyl alcohol,
n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, t-butyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, chloroform, carbon tetrachloride, benzene, toluene, xylene, N,N-dimethylformamide, dimethyl sulfoxide, ethyl ether , isopropyl ether, tetrahydrofuran, mixtures of two or more of these solvents. The fluorine-containing diepoxy compound thus obtained has extremely high utility as a water- and oil-repellent agent or a surfactant intermediate. That is, by homopolymerizing the fluorine-containing diepoxy compound or copolymerizing it with at least one type of other polymerizable epoxide, a water and oil repellent containing a perfluoroalkyl group in the side chain can be obtained. . Furthermore, a fluorine-containing diepoxy compound can be converted into a surfactant having a cationic group by ring-opening it with an amine. Furthermore, by opening the epoxy ring with sodium bisulfite, it can be converted into a surfactant having a sulfonate type anionic group. In addition, the fluorine-containing diepoxy compound obtained by the present invention can be used for various purposes such as paint additives, mold release agents, and plastic additives. Next, the present invention will be specifically explained with reference to Examples. Example 1 Perfluorooctane sulfonamide
499 g (1.0 mol) of C ₈ F ₁₇ SO ₂ NH ₂ , 1000 g of polyethylene glycol (average molecular weight 400) and 5.9 g of sodium chloride were added to a 4-neck, capacity 2, equipped with a stirrer, reflux condenser, thermometer and dropping funnel. It was placed in a round bottom flask. After heating until the internal temperature reaches 70℃ and the sodium chloride catalyst is dissolved,
277.6 g (3.0 mol) of epichlorohydrin was quickly added dropwise, and the mixture was heated and stirred for 4 hours while maintaining the internal temperature at 70°C. A sample of a portion of the reaction mixture was analyzed by gas chromatography and found to have the following composition. (The composition is indicated by the area ratio in the gas chromatogram. Also, the peak identification is by GC-
I did it with MS. ) After that, while keeping the liquid temperature in the reaction system at 70℃,
% CH ₃ ONa methanol solution (351.7 g) was added dropwise.
After the dropwise addition was completed, the mixture was cooled to room temperature, 1.5 parts of isopropyl ether and 1 part of distilled water were added, and the ether layer was separated. The ether layer was washed three times with 500 ml of 5% brine, dried over 120 g of anhydrous sodium sulfate overnight, and the isopropyl ether was distilled off and dried up to give 577 g of a yellow semi-solid. When this product is distilled under reduced pressure, the desired fluorine-containing diepoxy compound is obtained as the main distillate.

[Formula] 480g was obtained. Appearance White semi-solid C ₈ F ₁₇ SO ₂ NH ₂ Yield 78.6% Boiling point 123.0-129.0℃/0.4-0.45 mmHg IR spectrum 3350, 3180 cm ^-1 of C ₈ F ₁₇ SO ₂ NH ₂
NMR spectrum where absorption due to N-H stretching vibration of and N-H bending vibration of 1550 cm ^-1 disappears (carbon tetrachloride solvent TMS standard) (a) 3.1 and 3.4ppm (4H) (b) 3.8 and 4.0ppm (2H) (c) 2.5 and 2.7ppm (4H) Mass spectra

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[Table] Example 2 Perfluoroalkane sulfonamide mixture (component composition according to gas chromatography analysis is as follows: C ₄ F ₉ SO ₂ NH ₂ 1.6% C ₅ F ₁₁ SO ₂ NH ₂ 19.8% C ₆ F ₁₃ SO ₂ NH ₂ 71.0% C ₇ F ₁₅ SO ₂ NH ₂ 3.6% C ₈ F ₁₇ SO ₂ NH ₂ 3.9% (However, the composition is the area ratio of the peaks.) 199.5
g, polyethylene glycol (average molecular weight 400)
400 g and 2.1 g of lithium chloride were charged into a four-neck round bottom flask equipped with a stirrer, reflux condenser, thermometer, and addition funnel. After heating until the internal temperature reaches 65℃, add 138.8g of epichlorohydrin.
was quickly added dropwise, and the mixture was heated and stirred at 65°C for 3 hours. Thereafter, while maintaining the temperature inside the reaction system at 65° C., a 28% CH ₃ ONa methanol solution was added dropwise until the reaction mixture became slightly alkaline. It took
The amount of 28% CH ₃ ONa methanol solution was 175.2 g. After the dropwise addition was completed, the mixture was cooled to room temperature, 1 portion of isopropyl ether and 0.5 portions of distilled water were added, and the ether layer was separated. Furthermore, the ether layer was washed three times with 150 ml of 5% saline, and 100 g of anhydrous sodium sulfate was added.
After drying overnight, the isopropyl ether was distilled off and the mixture was dried to obtain 256.0 g of a colored liquid. When this is distilled under reduced pressure, a mixture of the desired fluorine-containing diepoxy compounds is obtained as the main distillate.
183.5g was obtained. Appearance Pale yellow liquid Boiling point 90.0-118.0℃/0.28mmHg Component composition ratio (peak area ratio) by GLC Example 3 Perfluorohexane sulfonamide
C ₆ F ₁₃ SO ₂ NH ₂ 79.8g (0.2 mol), methanol 200
ml and tetraethylammonium iodide 5.1g
A 4-necked round bottom flask with a capacity of 1 was equipped with a stirrer, reflux condenser, thermometer and addition funnel. After heating to the reflux temperature of methanol, 55.5 g (0.6 mol) of epichlorohydrin was quickly added dropwise, and heating and stirring was continued for 7 hours at the reflux temperature of methanol. Six hours after the dropwise addition of epichlorohydrin, a portion of the reaction mixture was sampled and subjected to gas chromatography analysis, and the composition was as follows. (The composition is indicated by the peak area ratio of GC. Peak identification was performed by GC-MS.) After that, while maintaining the liquid temperature in the reaction system at the reflux temperature of methanol, 28% CH ₃ ONa methanol solution was added.
72.0g was dropped. After the dropwise addition was completed, methanol was distilled off, the solution was dissolved in 200 ml of isopropyl ether, and the solution was washed three times with 100 ml of distilled water. Separate the ether layer,
After drying with 50 g of anhydrous sodium sulfate overnight, the isopropyl ether was distilled off and dry-applied.
106.2 g of a colored liquid was obtained. When this product is distilled under reduced pressure, the desired fluorine-containing diepoxy compound is obtained as the main distillate.

[Formula] 72.1g was obtained. Appearance Pale yellow liquid C ₆ F ₁₃ SO ₂ Yield based on NH ₂ 70.5% Boiling point 111.0-113.0℃/0.33mmHg n ²⁵ _D 1.3835 NMR spectrum (carbon tetrachloride solvent, TMS standard) (a) 3.1 and 3.3ppm (4H) (b) 3.8 and 3.9ppm (2H) (c) 2.5 and 2.7ppm (4H) Mass spectra

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[Table] Example 4 Perfluoroheptane carbonamide
C ₇ F ₁₅ CONH ₂ 82.6g (0.2mol), methanol 200
ml and tetraethylammonium iodide 5.1g
was charged into a 1 capacity 4-neck round bottom flask equipped with a stirrer, reflux condenser, thermometer and addition funnel. Methyl epichlorohydrin after heating to the reflux temperature of methanol

[Formula] 63.9 g (0.6 mol) was quickly added dropwise, and heating and stirring was continued for 7 hours at the reflux temperature of methanol. After that, while maintaining the liquid temperature in the reaction system at the reflux temperature of methanol, 28% CH ₃ ONa methanol solution was added.
72.0g was dropped. After the dropwise addition was completed, methanol was distilled off, the solution was dissolved in 200 ml of isopropyl ether, and the solution was washed three times with 100 ml of distilled water. Separate the ether layer,
After drying with 50 g of anhydrous sodium sulfate overnight, the isopropyl ether was distilled off and dry-applied.
109.9 g of a colored liquid was obtained. When this product is distilled under reduced pressure, the desired fluorine-containing diepoxy compound is obtained as the main distillate.

[Formula] 74.6g was obtained. Appearance Pale yellow liquid C ₇ F ₁₅ Yield based on CONH ₂ 67.5% NMR spectrum (carbon tetrachloride solvent TMS standard) (a) 3.1 and 3.3ppm (4H) (b) 1.2ppm (6H) (c) 2.5 and 2.7ppm (4H) Mass spectra

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Claims (1)

[Claims] 1 General formula (1) (In the formula, Rf is a perfluoroalkyl group containing 1 to 20 carbon atoms, Z is -SO ₂ - or -CO-, and R, R' and R'' are a hydrogen atom or a lower alkyl group. ) A fluorine-containing diepoxy compound represented by