JPS5942347A - Preparation of fluorine-containing quanternary ammonium salt - Google Patents

Abstract

PURPOSE:To obtain the titled compound capable of exhibiting improved ability to reduce the surface tension, and having improved chemical and heat resistance and further oil repellency, mold releasing property and foam stabilizing action, etc., by reacting a compound derived from a perfluoroalkenyl aryl ether with a tertiary amine. CONSTITUTION:Hexafluoropropene or an oligomer thereof is reacted with an aromatic compound having at least one or more hydroxy groups to give a perfluoroalkenyl aryl ether, which is then reacted with a mono- or dihalide of a dialkyl ether to afford a compound of formula I (n is an integer 1-3; Ar is aromatic group; m is 1 or 2; X is halogen). The resultant compound of formula I is further reacted with a teritiary amine, preferably having a 1-6C alkyl, benzyl, pyridyl or quinolyl group, etc., to give the aimed compound of formula II(T is quaternary ammonium residue).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing a fluorine-containing compound. More specifically, it relates to a method for producing a fluorine-containing compound in which a hydrophilic group is reacted with a new compound perfluoroalkenyl aryl ether obtained by the reaction of a hexafluoropropene oligomer with an aromatic compound having at least one hydroxy group. . This compound is particularly useful as a surfactant.

Conventionally, as typical fluorine-containing surfactants, there have been various derivatives using starting materials such as perfluorocarbonyl fluoride (C7F+ 50OF) and perfluorosulfonyl fluoride (08F+ 7302F), which are produced by electrolytic fluorination. Although commercially available, those having 6 or more carbon atoms useful as surfactants have extremely poor yields and are therefore very expensive, so their use is limited despite their excellent properties.

In addition, ω-human 1-perfluoroalcohol 1-1 (CF2 CF2 )n CH20 (1) obtained by telomerization of methanol and tetrafluoroethylene is used as the starting material, and perfluoroeye A-dite (R
There are also known starting materials such as r I (where Rf has a carbon number of 5 or more), but the former has hydrogen at the end, so its properties as a fluorine-containing surfactant are reduced. The latter also has the drawback that the reaction is complicated and the yield of the target product as well as the yield of the target product is unfavorable.

Furthermore, there are products that use tetrafluoroethylene oligomer as a starting material, but this method is difficult to handle because the raw material, tetrafluoroethylene, is extremely easy to polymerize, and even if the degree of polymerization is adjusted, the oligomer still has a low degree of polymerization. Since some products are produced in the form of wax-like substances with relatively high molecular weight, the yield of oligomers having a carbon number useful as surfactants is low.

The present inventors have previously made an invention in which perfluoroalkenyl aryl ethers can be obtained in good yield by reacting hexafluoropropene or an oligomer thereof with an aromatic compound having at least one hydroxyl group.

Accordingly, the present invention has been completed as a result of repeated research on fluorine-containing surfactants derived from perfluoroalkenyl aryl ethers.

In particular, the fluorine-containing surfactant according to the present invention exhibits an excellent ability to lower surface tension and has excellent chemical resistance and heat resistance compared to hydrocarbon surfactants. In particular, it has special properties that cannot be obtained with hydrocarbon surfactants, such as oil repellency, mold releasability, oil re-deposition prevention effect, and foam stabilizing effect. Therefore, these properties can be used as oil repellents, mold release agents, antifouling agents, antifogging agents, flotation agents, foaming agents, foam stabilizers, degreasing detergents, and the like. In addition, as products that utilize special properties, extremely crowded applications can be expected, such as foam extinguishing agents, oil collecting agents, penetrating agents, emulsion breaker-1 dyeing aids, plating additives, and emulsifiers for fluororesin emulsion polymerization. be. Moreover, the perfluoroalkenyl aryl ethers used in the present invention are, for example, disclosed in Japanese Patent Application No. 49-0269
As described in No. 59, it can be obtained in high yield and can be put to practical use at a reasonable price.

General formula used as a raw material for the fluorine-containing compound of the present invention: % formula %) [] In formula 1, Ar1c & an aromatic group that may have a substituent, X is a halogen, 0 is an integer of 1 to 3, and m represents 1 or 2. ] In the compound represented by the above, perfluoroalkenyl aryl ethers are first produced from hexafluoropropene or an oligomer thereof and an aromatic compound having at least one hydroxy group.

(Aromatic compounds having at least one hydroxy group here are, in principle, aromatic MPA hydrogen compounds having one or more hydroxy groups on an aromatic nucleus such as benzene, naphthalene, etc., with substituents such as alkyl groups and aryl groups. ,
It may have an acyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, a nido[1M1 halogen group, a cyano group, a sulfonic acid group, or an acid amide group having no active hydrogen.

In addition, the typical structure of the perfluoroalkenyl group of the perfluoroalkenyl aryl ethers obtained here is N
Based on MR analysis, it is estimated to be of the following formula.

(1) Perfluoropropenyl M: 5-CF3-CF=CF- (2) Perfluorohexenyl group: (3) Perfluorononenyl group: CF3゜) This was then induced into compound [11r'] by the following method. do.

Perfluoroalkenyloxyarylalkylene halides: mono- or civalides of perfluoroalkenyl aryl ether and dialkyl ether ((XI
(CH2) m O(CH2) mHl or (Xl
(CH2)I, lo)2: where m is 1 or 2
integer, X has the same meaning as above. Primarily, chloromethyl methyl ether is used. )−6= are reacted.

In the present invention, the compound represented by the above general formula [■'] and a tertiary amine are directly reacted to form a compound represented by the general formula: % formula %] [where T■ is a quaternary ammonium residue, m is 1 or The integer 2, Ar, X and n have the same meanings as above. The 4th ammonium salt shown by can be directly extracted. The constituent components of the quaternary ammonium salt include aliphatic amines, alkanolamines, alicyclic amines, aromatic amines, and heterocyclic compounds in which a ring-forming chamber is directly bonded to an alkylene group. The tertiary amine used has 1 to 1 carbon atoms.
6 alkyl group, alkanolamine having 1 to 4 carbon atoms,
benzyl group, piperidino group, pyridyl group, quinolyl group,
Those having a 2H-pyrrolyl group and the like are preferred, but are not limited thereto.

The present invention will be explained below with reference to Examples.

Example 1 p-perfluorononenyloxybenzylpyri (1) p
-Production method of perfluorononenyloxybenzyl chloride: p-perfluorononenylphenyl ether 52.4a
(0.1 mol) to 45.0 glacial acetic acid (+ (0°7
5 mol), ferric chloride 24.3a (0.15 mol)
, monochlorodimethyl ether 19.450 (0,22
mol) and stirred and reacted at 70°C for 72 hours. The end point of the reaction is confirmed by the disappearance of the p-perfluorononenylphenyl ether peak using a gasket graph. Pour the reaction product into water, separate the insoluble liquid, and distill it under reduced pressure. Boiling point 86.5-87.0℃/1.5111ml
-1 (l fraction (colorless transparent liquid) 56.1 (1 (yield 9
．． 8%) is obtained. This fraction shows a single peak on gas chromatography. Elemental analysis: F56.80%
(calculated value 56.39%), infrared absorption spectrum analysis; it can be confirmed that it is fluorononenyloxybenzyl chloride.

(2) 14.8 (1 (0.02 mol)) of p-perfluorononenyloxybenzyl chloride was added to 1 part of diethyl ether.
Pyridine 1.58 (]
(00.02 mol is added and reacted with stirring for 24 hours under reflux of ether. The reaction product precipitates out, so it is separated by filtration and recrystallized with methanol to form pale yellow crystals 15.4011 (94% ) is obtained.As a result of infrared absorption spectrum analysis, it is confirmed that it is p-perfluorononenyloxybenzylridinium chloride.

Example 2 The surface tension of each surface tension was measured by changing the concentration of the fluorine-containing surfactant obtained in Example 1. The measurement was carried out using the Wilhelmi method, the temperature was 25° C., and the target glass plate was used. The results are shown in Table-1.

9- - 10'-

Claims (1)

[Claims] 1. General formula: % formula %) [] [In the formula, n is an integer of 1 to 3, Ar is an aromatic group, ■ is 1 or 2, and X represents a halogen; A general formula characterized by reacting a compound represented by the following with a tertiary amine: %Formula% [In the formula, T is a quaternary ammonium salt residue, n, m, A
r and X have the same meanings as above]
A method for producing class ammonium salt.