JPH11302242A - Fluorine-containing quaternary ammonium salt - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound excellent in heat stability as well as surface modifying properties such as electron charge controlling property and static charge-preventing property and useful as a water-repelling and oil-repelling agent. SOLUTION: This compound is represented by the formula [R1 is a 1-5C alkylene; R2 and R3 are each a 1-3C alkyl or phenyl; X is a halogen, CH3 COO or the like], e.g. ethyl tridecafluorooctanoate. Furthermore, the compound is preferably obtained by reacting, e.g. perfluorohexene with ethyl chloroacetate and potassium fluoride in dimethylformamide in the presence of potassium iodine catalyst, hydrolyzing the resultant compound in ethanol in the presence of potassium hydroxide, reacting the resultant compound with thionyl chloride under anhydrous conditions, reacting the resultant compound with a terminal dimethylamino group-containing alkylamine and reacting the resultant tridecafluorooctanoic acid amide-containing terminal dimethylamino group with methyl halide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a water / oil repellent, a fiber softener, a charge control agent, an antistatic agent, a release agent, an antifouling agent, and a surface modifier for other resins, metals, woods and the like. A useful fluorine-containing quaternary ammonium salt.

[0002]

2. Description of the Related Art It has been known that compounds having a perfluoroalkyl group or a perfluoroalkenyl group have excellent water and oil repellency. In particular, quaternary ammonium salts having the above functional groups are known to exhibit excellent effects as softeners for fibers and the like. For example, fluorine-containing surfactants described in JP-A-57-164198 and fluorine-containing pyridinium salts found in JP-A-59-42347 can be mentioned. However, these have problems in stability at high temperatures due to structural problems.

[0003]

SUMMARY OF THE INVENTION The present inventor has made intensive studies to solve the problems of the prior art as described above. As a result, a new fluorinated quaternary ammonium salt having excellent thermal stability as well as excellent charge controllability and antistatic properties as compared with conventional fluorinated quaternary ammonium salts can be obtained. I found it.

[0004]

The present invention provides a compound represented by the following general formula (1):

[0005]

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The present invention provides a fluorine-containing quaternary ammonium salt represented by the formula:

In the formula, R1 represents an alkylene group having 1 to 5 carbon atoms, and R2 and R3 represent an alkyl group having 1 to 3 carbon atoms and a phenyl group, which may be the same at the same time. . X is a halogen atom, CH ₃ COO, CF ₃ COO, BF ₄ , BPh
_{4, PO 4 · n (WO} 3), CH 3 PhSO 3, CF 3 SO 3, CH 3 SO 3, PhSO 3,
Shows HPO ₃ , HSO ₄ , NO ₃ and OH.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to a compound represented by the general formula (1)
The perfluoroalkyl group represented by F13- is generally obtained as a dimer of hexafluoropropene.

[0009] In the general formula (1), R1 has 1 to 1 carbon atoms.
5, preferably 2 to 4 alkylene groups.

In the general formula (1), R2 and R3 represent the number of carbon atoms
It represents 1-3 alkyl groups and phenyl groups, and may be the same at the same time. Preferably, it is an alkyl group having 1 to 2 carbon atoms.

X in the general formula (1) is a halogen atom, CH
₃ COO, CF ₃ COO, BF ₄ , BPh ₄ , PO ₄・ n (WO ₃ ), CH ₃ PhSO ₃ , C
F ₃ SO ₃ , CH ₃ SO ₃ , PhSO ₃ , HPO ₃ , HSO ₄ , NO ₃ and OH are shown. Preferably, Cl, Br, I, CF ₃ COO, BF ₄ , BPh ₄
And PO ₄ · n (WO ₃ ).

Although the method for producing the fluorinated quaternary ammonium salt represented by the general formula (1) is not particularly limited, the following production example is mentioned as a simple method.

First, ethyl tridecafluorooctanoate is obtained by reacting a dimer of hexafluoropropene, perfluorohexene, ethyl chloroacetate and potassium fluoride in dimethylformamide in the presence of a potassium iodide catalyst. Can be Hydrolysis of this ethyl tridecafluorooctanoate in ethanol in the presence of potassium hydroxide gives tridecafluorooctanoic acid. By reacting this tridecafluorooctanoic acid with thionyl chloride under anhydrous conditions, tridecafluorooctanoic acid chloride can be obtained. The tridecafluorooctanoic acid amide having a terminal dimethylamino group can be obtained by reacting this tridecafluorooctanoic acid chloride with an alkylamine having a terminal dimethylamino group in a suitable solvent. The desired fluorinated quaternary ammonium salt can be obtained by reacting the terminal dimethylamino group-containing tridecafluorooctanoic acid amide with methyl halide in a suitable solvent. By adding a large excess of a suitable salt of this fluorinated quaternary ammonium salt in acetonitrile, a fluorinated quaternary ammonium salt having various counter ions can be obtained.

The product obtained by the above-mentioned production method may be purified by distillation, recrystallization or column chromatography, if desired.

[0015]

Examples are shown below. Note that the present invention is not limited to only the following examples.

Example 1 Synthesis of ethyl tridecafluorooctanoate (compound 1) In a 3 liter flask, 825.11 g (2.75 g) of hexafluoropropene dimer perfluorohexylene was added.
mol), 308.8 g (2.5 mol) of ethyl chloroacetate, 203.35 g (3.5 mol) of potassium fluoride, 46.17 g (0.125 mol) of tetrabutylammonium iodide, and 2 liters of dimethylacetamide, and heated at 50 ° C. While stirring for 24 hours. After completion of the reaction, the reaction solution was poured into 15 liters of water and sufficiently stirred, and the upper aqueous phase was removed. The bottom was washed three times with 10 liters of yellow oil remaining in water and twice with one liter of aqueous sodium sulfite. After washing twice with 1 liter of water again, water was removed with magnesium sulfate. Pyridine 2 is added to the obtained oil.
After adding 0 ml and stirring for 2 hours, the mixture was washed three times with 1 liter of water, and water was removed with magnesium sulfate.
Passed through a column packed with 00g. The crude product after the treatment was distilled to obtain 568.4 g of ethyl tridecafluorooctanoate (yield: 56%).

Example 2 Synthesis of tridecafluorooctanoic acid (compound 2) In a 2 liter flask, 284.20 g (0.7 mol) of ethyl tridecafluorooctanoate obtained in Example 1 was added.
55.45 g (0.84 mol) of potassium hydroxide and 700 ml of ethanol were added and refluxed for 2 hours. Ethanol was distilled off from this reaction vessel by heating, and the residue was allowed to cool to room temperature.
0 ml was added for extraction. Take out the organic phase and 200ml
Was washed twice with water, and chloroform was distilled off from the washed organic phase under reduced pressure. The crude product after the treatment was distilled under reduced pressure to obtain 185 g of tridecafluorooctanoic acid (yield: 70%).

Example 3 Synthesis of tridecafluorooctanoic acid chloride (compound 3) In a 500 ml flask, 151.23 g (0.40 mol) of tridecafluorooctanoic acid obtained in Example 2 and 58 ml (0.80 mol) of thionyl chloride were obtained. And dimethylformamide 3m
l (0.04 mmol) was added and refluxed for 3 hours. After completion of the reaction, the remaining thionyl chloride was distilled off, and the residue was distilled under reduced pressure to remove tridecafluorooctanoic acid chloride.
13 g were obtained (yield: 71%).

Example 4 Synthesis of N- [3- (dimethylamino) propyl] tridecafluorooctanoic acid amide (Compound 4) The tridecafluorooctanoic acid chloride obtained in Example 3 was placed in a 2 liter flask. 05g
(0.285 mol) and 800 ml of ethanol were added, and N, N-dimethyl-1,3 diaminopropane 29.1 was added while stirring under ice cooling.
A solution of 2 g in 200 ml of ether was added dropwise over 15 minutes, and the mixture was stirred for 1 hour. After the temperature was raised to room temperature and further stirred for 1 hour, the reaction solution was poured into 1 liter of a 0.3 N aqueous solution of sodium hydroxide, and sufficiently stirred to remove the aqueous phase. The organic phase was washed twice with 500 ml of a saturated saline solution, and after removing water with magnesium sulfate, the organic solvent was distilled off under reduced pressure to give crude N- [3- (dimethylamino) propyl] tridecafluorooctanoic acid amide. Thing was obtained.

Example 5 1- (Fluorohexyl) acetoxyamido-propyl-3-
(N, N, N-tetramethylammonium iodide (compound
Synthesis of 5) In a 2-liter flask, the N- [3-
(Dimethylamino) propyl] tridecafluorooctanoic acid amide in crude product and acetonitrile 2
Of methyl iodide 4 while stirring under ice-cooling.
0.45 g was added dropwise. After stirring for 1 hour, perform filtration,
The obtained solid was recrystallized from acetonitrile to give 1- (fluorohexyl) acetoxyamido-propyl-
3- (N, N, N-tetramethylammonium iodide is 12
9.17 g were obtained (two-step yield from tridecafluorooctanoic acid chloride: 75%).

Example 6 1- (Fluorohexyl) acetoxyamido-propyl-3-
(Synthesis of N, N, N-tetramethylammonium phosphotungstate (Compound 6)) In a 5-liter flask, 1- (fluorohexyl) acetoxyamido-propyl-3- (N , N,
129.17 g of N-tetramethylammonium iodide (0.
21mol) and 3 liters of ion-exchanged water, 70 ℃
Phosphotungstic acid hydrate 63 while heating and stirring with
An aqueous solution obtained by dissolving 3.6 g (0.22 mol) in 500 ml of ion-exchanged water was added dropwise. After stirring at 70 ° C. for 30 minutes, the reaction vessel was cooled with ice and the reaction solution was filtered. The obtained solid was recrystallized from acetonitrile aqueous solution to give 1- (fluorohexyl) acetoxyamido-propyl-3- (N, N, N-
Tetramethylammonium phosphotungstate is 2
88.76 g was obtained (yield: 43%).

Example 7 1- (Fluorohexyl) acetoxyamido-propyl-3-
(Synthesis of N, N, N-tetramethylammonium tetrafluoroboron salt (compound 7)) In a 1 liter flask, 1- (fluorohexyl) acetoxyamido-propyl-3- (N , N,
101.00 g of N-tetramethylammonium iodide (0.
167 mol) and 300 ml of ion-exchanged water were added, and an aqueous solution in which 36.8 g (0.335 mol) of tetrafluoroboron sodium salt was dissolved in 100 ml of ion-exchanged water was added dropwise while heating and stirring at 70 ° C. After stirring at 70 ° C. for 3 hours, the reaction solution was filtered, and the obtained solid was recrystallized from an acetonitrile / hexane mixed solution to give 1- (fluorohexyl) acetoxyamido-propyl-3- (N, N, N- 64.4 g of tetramethylammonium / tetrafluoroboron salt was obtained (yield: 67.2%).

Table 1 shows the physical properties of the products of Examples 1-3 and 5-7.

[0024]

[Table 1]

The ¹ H of the products (1) to (3) in Table 1
Shows the assignment position of -NMR and ¹⁹ F-NMR.

[0026]

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[0027]

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[0028]

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[0029]

The compound of the present invention is a novel fluorine-containing compound, has excellent stability at high temperatures as compared with conventional products, and has a water and oil repellent, a fiber softener, a charge controlling agent, a release agent, and a protective agent. It is useful as a surface modifier for resins such as soiling agents, metals and wood.

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──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI D06M 13/46 D06M 13/46 // C09K 3/00 112 C09K 3/00 112E 3/16 104 3/16 104E 3/18 103 3/18 103 C10M 105/68 C10M 105/68 C10N 40:36 (72) Inventor Masashi Takeshita 3-1-2 Isobe-dori, Chuo-ku, Kobe-shi, Hyogo Prefecture Neos Co., Ltd.

Claims (1)

[Claims] 1. General formula (1): (Wherein, R 1 represents an alkylene group having 1 to 5 carbon atoms;
R2 and R3 represent an alkyl group having 1 to 3 carbon atoms and a phenyl group, and may be the same at the same time. X is a halogen atom, CH ₃ COO, CF ₃ COO, BF ₄ , BPh ₄ , PO ₄ .n (WO ₃ ), C
H ₃ PhSO ₃ , CF ₃ SO ₃ , CH ₃ SO ₃ , PhSO ₃ , HPO ₃ , HSO ₄ , NO ₃ and OH are shown. ) A fluorinated quaternary ammonium salt represented by).