JPS6022699B2 - Hexafluoropropene oligomer derivative - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a fluorine-containing compound obtained by reacting a hexafluoroproben oligomer with an alkylamine having an oxyethylene group, and salts thereof.

A fluorine-containing nonionic surfactant in which a hydrophobic residue is bonded to the end of an oxyalkylene group directly linked to a perfluoroalkylene group has already been reported (Akira Tokuseki -
49 spot y).

However, no tertiary amine-containing fluorine-containing compounds having an oxyethylene group are known.

An object of the present invention is to utilize the characteristics of a fluorine-containing compound having an oxyalkylene group as a surfactant, introduce an ionic group thereto, and provide a compound having a wider range of uses. A surfactant having an oxyalkylene group, that is, a nonionic surfactant, has a major feature in that its HLB can be arbitrarily adjusted by changing the number of moles of the oxyalkylene group. On the other hand, cationic or amphoteric surfactants can achieve effects that cannot be obtained with nonionic surfactants in various fields such as disinfectants, disinfectants, acid solution additives, softeners, antistatic agents, coloring aids, and many others. It is widely used. The present invention relates to a compound for providing a cationic or amphoteric surfactant whose HLB can be arbitrarily changed in addition to the basic properties of a fluorine-containing surfactant such as low interfacial tension and low foaming properties.

That is, the present invention has the general formula: Rf-A-Q [wherein, Rr is a perfluoroalkenyl group having 6 or 9 carbon atoms derived from hexafluoroprobene, A is an oxyethylene group or a polyoxyethylene group, Q represents a tertiary amine, tertiary amate salt, quaternary ammonium salt, betaine or amine oxide residue having an alkyl group having 3 or less carbon atoms].

The compound of the present invention can be obtained by reacting a hexafluoroproben oligomer, an oxyethylene group, and a dialkylethanolamine having an alkyl group having 3 or less carbon atoms.

The tertiary amine obtained may be converted into a di salt, an ammonium salt, an amine oxide or a betaine by conventional methods. The hexafluoroproben oligomer used in the present invention may be produced by the method described in Tokokukan Sho 50-1117705. Preferred oligomers are those having 6, 9 or 12 carbon atoms, and oligomers having 6 or 9 carbon atoms are particularly preferred because they are excellent in industrial productivity. Alkylamines having an oxyethylene group mean dialkyl ethanolamines or ethylene oxide adducts thereof.

When the compound of the present invention is used as a surfactant, preferable dialkylethanolamines include those having a lower alkyl group and an oxyethylene group, such as dimethylethanolamine, methylethylethanolamine, diethylethanolamine, and dipropylethanolamine. The group is preferably 3 or less. When ethylene oxide is added to dialkylethanolamine, it is appropriate to carry out addition polymerization in an amount of 1 to 50 moles, preferably 1 to 20 moles, of ethylene oxide per mole of dialkylalkanolamine. The number of moles added may be arbitrarily adjusted depending on the purpose of use. The reaction of ethylene oxide to jetanolamine may be produced by a conventional method.

The compound of the present invention can be easily obtained by reacting a hexafluoroproben oligomer with a dialkyl alkanolamine or its ethylene oxide adduct in the presence of a proton acceptor at room temperature.

Preferred proton acceptors are tertiary amines and alkalis such as potassium carbonate, but the dialkylamine itself may be used in excess for the reaction. The obtained tertiary amine itself has an excellent surface-active effect, but it may be further quaternized, betainated, or oxidized.

These may be manufactured using a conventional method. For example, for acid salts, the obtained tertiary amine may be neutralized with an appropriate acid such as hydrochloric acid, sulfuric acid, acetic acid, etc., and for quaternization, the tertiary amine may be neutralized with a quaternizing agent,
For example, it may be reacted with methyl iodide or the like. For betaination, the tertiary amine is treated with a betaination agent such as monochrome sodium acetate, 8-propiolactone, propane sultone, or the like. Amine oxide can be obtained by treating a tertiary amine with hydrogen peroxide. As mentioned above, the compound of the present invention is typically used as a surfactant, and in particular, it can provide a cationic or amphoteric fluorine-containing surfactant whose HLB can be arbitrarily adjusted.

Particularly useful applications include extinguishing agents for oil fires, fiber treatment agents, metal-containing surface treatment agents, template agents, antistatic agents, disinfectants, and resin modifiers for kneading. Example 1 N-(2-perfluorononenyloxyethyl)-N.
N.N-trimethylammonium iodide [C9
F,7-○-CH2CH2N (CH3)3]・lem
Production method: In a three-necked flask equipped with a reflux condenser and a reflux condenser, 30 minutes of acetonitrile and 36.5 hours (0.4 mol) of N.N-dimethylethanolamine were dissolved, and the reaction layer was dissolved in a water bath for 25 hours. The third base of hexafluoroprobene oligomer was heated to 90.5 m (0.5 m) while cooling to ~35 mn.
2 mol) over a period of 5 hours.

The end point of the reaction was confirmed by gas chromatography when the oligomer disappeared. The reaction layer is divided into two layers, so take out the lower layer and wash it with alkaline water containing caustic soda.
Next, it is washed several times with fresh water to remove the water-impregnable portion, which is then distilled. Boiling point 48.0-49. A yellow liquid (yield 71.5%) with a weight of 0/2 Hg was obtained. This product showed almost a single peak in gas chromatography analysis. Infrared absorption spectrum analysis: Absorption based on C-F 7.6-9.4μ The analysis results show that the product is N-(2-perfluorononenyloxyethyl)-N・N-dimethylamine (C9F,7-○
It can be confirmed that -CH2CH is (C is) 2).

The N-(2-perfluorononenyloxyethyl)-N.N-dimethylamine thus obtained was 26 hours (0.0
5 moles) was dissolved in 75 moles of diethyl ether, further 8.4 moles (0.059 moles) of methyl iodide was added, and
The reaction was carried out for 4 hours while maintaining the temperature at 5 to 6° C. in a three-necked flask equipped with a reflux condenser, and the reactant was separated out of the system. This was fractionated using a rotor, and a brown waxy substance N1 (2
-perfluorononenyloxyethyl)-N・N・N-
28.1 hours of trimethylammonium iodide (yield: 85.0%) was obtained. ■ The surface tension and foaming properties of the product are as follows.

Surface tension 0.1% W/W): 24. y ratio/enemy 0.05%W'W): 30. y fertilizer/enemy 0.01%W/W): 44. (Measured using the Wilhelmi method at a liquid temperature of 25 qo) Super foaming: 0.1% W/W) Take 25 ml of aqueous solution in a 50 ml cylinder and shake vigorously at a liquid temperature of 25 q. The foam disappears immediately after release, and the foaming property is extremely low.

Example 2 N-(2-perfluorononenyloxyethyl)-N.
N-dimethylbetaine '11 Production method N-(2-perfluorononenyloxyethyl)-N.N-dimethylamine 29 (0.056 mol) obtained in the same manner as in Example 1 [1'], sodium monochloroacetate 8
5 mols (0.073 mol) and 10 mols of water were placed in a three-necked flask equipped with a reflux condenser and heated in an oil bath, and allowed to react under reflux for 14 hours.

The end point of the reaction was confirmed by gas chromatography when N-(2-perfluorononenyloxyethyl)-N.N-dimethylamine disappeared. After the reaction was completed, water was removed from the reaction layer using an evaporator, followed by extraction with absolute ethanol, and the ethanol was removed to form a pale yellow solid substance, N-(2-perfluorononenyloxyethyl)-N-N-dimethylbetaine. 62 (yield 95%) was obtained. Results of infrared absorption spectrum analysis of the product: Absorption occupied by C-F 7.6-9.4 μm Absorption occupied by COOe 6.12A Based on C day Absorption 3.4 peaks [2' Surface tension 0 , 1% W/W): 24, My fertilizer/enemy 0.05% W/W): 24, Target y/enemy 0.01%.

W/W): 24, My ship/enemy (however, Wilhelmi method,
Measured at a liquid temperature of 2500℃) Example 3 N-(perfluorononenyloxy polyoxyethylene)-N・N・N-trimethylammonium iodide (C9F,7-(C-CQC day 2),..3N Yu (CH3)3・le)'1
'Manufacturing method Polyoxyethylene-N・N-dimethylamine ((CH3)2N(CH2C)
About 0),. ．． 3H) Add 21.7 mmoles (0.M mol), 50 mmoles of methyl ethyl ketone, and 8.3 mmoles (0.06 mols) of potassium carbonate, and stir the hexafluoroproben oligomer triplex while heating at room temperature. 5 yen (0.05 mol) about 30
The rope continues for a minute, and then performs rope worship for another two minutes.

The end point of the reaction was determined by infrared absorption spectrum analysis.
This was confirmed by the disappearance of the absorption of Filter the reaction layer,
The methyl ethyl ketone layer was separated and the methyl ethyl ketone was removed to obtain 36.0 g of a brown liquid N-(perfluorononenyloxy polyoxyethylene)-N.N-dimethylamine. Infrared absorption spectrum analysis: Absorption occupied by C-F 7.6-9.6 μm Absorption based on 3.4-Furthermore, the N-(perfluorononenyloxy polyoxyethylene ) 19.4 moles (0.02 mol) of N-N-dimethylamine and tetrahydride.

Add methyl uride (0.4 mol) of furan 50 to a three-necked flask equipped with a rope strainer and reflux condenser, and continue the reaction by controlling the overflow from the outside to 5 to 6°C. . The reaction state of methyl iodide was followed by gas chromatography, and the reaction was continued for 8 hours until the reaction stopped.
Thereafter, the reaction layer was transferred to an evaporator, and the volatile portion was distilled off to obtain a gray-brown viscous liquid of N-(perfluorononenyloxy polyoxyethylene)-N,N,N-trimethylammonium iodide. I got it. [21 Surface tension 0.1% W/W): Shigeru. gym' enemy 0.01% W/W): 24. Example 4 (Surface tension test) The surface tension of the aqueous solution of the compound of the present invention was Wilhelmi method (25
Table 1 shows the results measured in qo).

Table-I Example 5 (Twill oiliness test) 0.1% (weight/weight) of the compound obtained in Examples 1 and 2
Volume) Soak cotton in the aqueous solution, dry at 120 pm for 3 minutes, and drop Nujol oil drops on it.

It did not pass through the oil register even after 2 hours.

Example 6 (Antistatic Hall Test) Since the compounds of the present invention have excellent insulating properties due to their perfluorocarbon groups, there are generally few compounds with excellent antistatic ability, but Examples 1 and 2
A 0.1% (wt/vol) ethanol solution of the compound obtained in is applied onto sheets of rigid polyvinyl chloride and polymethyl methacrylate.

After drying this at room temperature, rub it twice with tissue paper. The results are shown in Table-2. Table 2 (Measurement conditions: 25°C, humidity: 65*) Example 7 (Nutrility test) Apply a 0.2% (weight/volume) ethanol solution of the compounds [41 and 7] of Example 4 to the mold. do.

Claims (1)

[Claims] 1 General formula R_f-A-Q [In the formula, R_f is a perfluoroalkenyl group having 6 or 9 carbon atoms derived from hexafluoropropene, A is an oxyethylene group or a polyoxyethylene group, Q represents a tertiary amine, tertiary amate salt, quaternary ammonium salt, betaine or amine oxide residue having an alkyl group having 3 or less carbon atoms.