JPS5937000B2 - Method for producing fluorine-containing compounds - Google Patents

Description

[Detailed description of the invention] The present invention relates to a novel method for producing a fluorine-containing compound.

More specifically, it is a novel compound obtained by reacting a hexafluoropropene oligomer with an aromatic compound having at least one hydroxyl group.A fluorine-containing compound obtained by reacting a perfluoroalkenyl aryl ether with a group having hydrophilic properties. Concerning a method for producing a compound. This compound is particularly useful as a surfactant. Conventionally, typical fluorine-containing surfactants include perfluorocarbonyl fluoride (C7F15) obtained by electrolytic fluorination.
COF) and perfluorosulfonyl fluoride (COF) and perfluorosulfonyl fluoride (COF)
Various derivatives using C8F17S02F) as starting materials are commercially available, but those with 6 or more carbon atoms, which are useful as surfactants, have extremely poor yields and are therefore very expensive. Despite its characteristics, its use is limited.

In addition, ω-H-perfluoroalcohol (H
(CF2CF2)nCH2OH) as a starting material and perfluoroiodide (Rfl, where Rf has 5 or more carbon atoms) are known as starting materials, but the former has hydrogen at the end. However, the latter has the drawback that its properties as a fluorine-containing surfactant are reduced, and the latter also has a complicated reaction, resulting in undesirable yields of both the product itself and the derivatives of the daily products.

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 the oligomer still has low polymerization even if the degree of polymerization is adjusted. Since some of them are produced in the form of wax-like substances with a relatively high molecular weight, they have the drawback that the yield of oligomers having a carbon number useful as a surfactant 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 various compounds derived from perfluoroalkenyl aryl ether. In particular, when the fluorine-containing compound according to the present invention is used as a surfactant, it exhibits superior ability to lower surface tension and has superior chemical resistance and heat resistance compared to hydrocarbon surfactants. Are better.

In particular, it provides oil repellency and release properties that cannot be obtained with hydrocarbon surfactants. It has special properties such as compatibility, oil re-deposition prevention effect, foam stabilization effect, etc. Therefore, there are uses such as oil repellents, mold release agents, antifouling agents, antifogging agents, flotation agents, foaming agents, foam stabilizers, and degreasing detergents that utilize these properties. In addition, products that utilize special properties include foam extinguishing agents, oil collecting agents, penetrating agents, emulsion breakers, dyeing aids, plating additives,
It can be expected to have an extremely wide range of uses, such as emulsifiers for emulsion polymerization of fluororesin. Moreover, the perfluoroalkenyl aryl ethers used in the present invention are, for example,
As described in No. 026959, 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: [In the formula, Ar is an aromatic group that may have a substituent, Q is a carbonyl group, methylene group, or ethylene group, X is chlorine, bromine, n represents an integer from 1 to 3.

In the compound represented by ], perfluoroalkenyl aryl ethers are first produced from hexafluoropropene or its oligomer and an aromatic compound having at least one hydroxy group.

(Aromatic compounds having at least one hydroxy group here are, in principle, aromatic hydrocarbon compounds having one or more hydroxy groups on an aromatic nucleus such as benzene or naphthalene, and substituents such as alkyl or aryl groups. , an acyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, a nitro group, a halogen group, a cyano group, a sulfonic acid group, or an acid amide group having no active hydrogen. The typical structure of the perfluoroalkenyl group of alkenyl aryl ethers is estimated to be that of the following formula by NMR analysis. (
1) Perfluoropropenyl group: CF, -CF=CF-(2) Perfluorohexenyl group: ν ↓ 0 (3) Perfluorononenyl group: Next, this is induced into the compound [] by the following method.

(1) Perfluoroalkenyloxyarylalkylene halides: Mono- or dihalides of perfluoroalkenyl aryl ether and dialkyl ether ((
X1(CH2)MO(0H2)MHl or (X,(C
H2)MO)MO)2; where m is an integer of 1 or 2,
X has the same meaning as above.

Primarily, chloromethyl methyl ether is used.
) to react. (2) Perfluoroalkenyloxyarylcarbonyl halides: hexafluoropropene or hexafluoropropene oligomer and hydroxyarylcarboxylic acid phenyls (HO-Ar-CO
OC6H,; in the formula, Ar has the same meaning as above.

Mainly phenyl p-hydroxybenzoate is used. ) to obtain phenyl perfluoroalkenyloxyarylcarboxylate, which is then hydrolyzed and the resulting carboxylic acid is treated with thionyl halide. In order to react the compound represented by the general formula [] with an alkylene glycol or polyalkylene glycol or their monoalkyl ethers, an alcoholade of a glycol and an alkali metal is generally used. The formation of chloride can also be carried out without a catalyst.

Here, alkylene glycols having an alkylene group having 2 to 4 carbon atoms can be used, but preferably 2 carbon atoms are used.
Further, the number of carbon atoms in the alkyl group of the alkyl ether is preferably 1 or 2. In some cases, it is also possible to disperse the above-mentioned glycols and a deoxidizing agent, such as potassium carbonate, in a solvent, and dropwise react the compound represented by the general formula []. The obtained compound may be converted into a sulfuric acid ester or a phosphoric acid ester by a conventional method. This will be described in detail in Examples below.

Example 1 Polyoxyethylene perfluorononenyloxybenzoate (C9Fl7OC6H4COO(CH2C
H2O)NH) production method: (1) Production method of p-perfluorononenyloxybenzoyl chloride: 56.8y (0.1 mol) of p-perfluorononenyloxybenzoic acid to 35.79y (0.1 mol) of thionyl chloride .3 mol) and stirred at room temperature for 1 hour (the end point of the reaction is confirmed by gas chromatography when the peak of p-perfluorononenyloxybenzoic acid disappears).

Pour the reaction product into water, separate the insoluble material, and distill it under reduced pressure. 58.01 of a fraction (colorless transparent liquid) with a boiling point of 96.5 to 97.0°C/0.5 mmHg is obtained (yield: 99
%). Elemental analysis; F55.5O% (calculated value 55.05%
). Infrared absorption spectrum: C-F7.5-9.5μ (broad absorption), o; 6.27μ, 6.70μ, C = O
; 5.60μ, 5.66μ. From the above results, p-perfluorononenyloxybenzoyl chloride is confirmed. (2) Perfluorononenyloxybenzoyl chloride 11.71 (0.02 mol) obtained in the above (1) and polyethylene glycol (average molecular weight 1,000
)30y (0.03 mol) at 80°C with stirring.

Continue the reaction until the generation of hydrochloric acid gas stops. The end point of the reaction is confirmed by gas chromatography. The reaction was completed in about 5 hours, and this was converted into 1,1,2-trifluoro-1,2,2
-Extract with trichloroethane. White waxy substance 2
9.89 (yield 96%) is obtained. Infrared absorption spectrum analysis confirms that it is polyoxyethylene perfluorononenyloxybenzoate. Example 2 Methoxy polyoxyethylene perfluorononenyloxybenzyl ether (C9Fl7OC6H4CH2
Production method of O(CH2CH2O)NCH3): (1) p-
Production method of perfluorononenyloxybenzyl cucaride: p-perfluorononenyl phenyl ether 52.4
g (0.1 mol), 45.09 (0.75 mol) of glacial acetic acid, 24.39 (0.15 mol) of ferric chloride, and 19.45 g (0.22 mol) of monochlorodimethyl ether were added and heated at 70°C. The mixture was stirred and reacted for 72 hours.

The end point of the reaction is confirmed by gas chromatography by the disappearance of the p-perfluorononenylphenyl ether peak. Pour the reaction product into water, separate the insoluble liquid, and distill it under reduced pressure. Boiling point 86.5-87.0℃/1.5mm
Hg fraction (colorless transparent liquid) 56.19 (yield 98%)
is obtained. This fraction shows a single peak on gas chromatography. Elemental analysis; F56.8O% (calculated value 56.39%), infrared absorption spectrum analysis; C-F
7.5~9.5μ (wide absorption), ゜6.27μ, 6
．． 70μ. From the above results, it can be confirmed that it is D-perfluorononenyloxybenzyl chloride. (2)
Add 1.29 (0.03 mol) of sodium hydroxide to 33 g (0.03 mol) of polyethylene glycol monomethyl ether (average molecular weight 1100) and heat at 120'C.
Dehydrate.

To this was added 11.459 (0.02 mol) of perfluorononenyloxybenzyl chloride obtained in (1) of Example 2, and the mixture was stirred and reacted at 80'C for 24 hours. The end point of the reaction is confirmed by gas chromatography. 1 reactant
, 1,2-trifluoro-1,2,2-trichloroethane to give a white waxy substance 42.29% (yield 9
5ch) is obtained. The target compound is confirmed by infrared absorption spectrum analysis. Examples regarding the general properties and special performance of the fluorine-containing compound obtained by the present invention will be given below.

Example 3 Polyoxyethylene (2
A foaming power test was conducted using the Ross Miles method using 2.3 mol) perfluorononenyloxybenzoate ester.

The surfactant concentration was 0.1% (measurement temperature 40°C), and ammonium lauryl sulfate and sodium oleate were used as comparative samples. The results are shown in Table-1. Example 4 -C campus using the fluorine-containing surfactant of Example 1
Penetration power was measured by the disk method (concentration 0.1%, temperature 2
3℃).

The results are shown in Table-2. Example 5 The surface tension was measured by varying the concentration of the fluorine-containing surfactant obtained in Example 1 (measurement was performed using the Wilhelmi method, temperature: 25° C., object: glass plate).

Example 6 (oil re-deposition prevention test)
Clean metal pieces in a degreasing solution containing 01 (F6 (weight/volume)) and contaminated oil.

Pull up the metal piece and observe it with the naked eye. It can be seen that almost no mineral oil adheres, and re-adhesion of oil is prevented. When using a hydrocarbon surfactant, the oil removed by cleaning adheres to the metal piece again, resulting in incomplete cleaning. Example
7 (Mold releasability) Fluorine-containing surfactant obtained in Examples 1 and 2 0.2
% (weight/volume) aqueous solution is applied to the formwork.

Claims (1)

[Claims] 1 General formula: C_3nF_6n_-_1-O-Ar-Q-X [III]
[In the formula, n is an integer of 1 to 3, Ar is an aromatic group, Q is a carbonyl group, methylene group or ethylene group, and X represents bromine or chlorine] and alkylene glycol, polyalkylene glycol or A method for producing a fluorine-containing compound, which comprises reacting these monoalkyl ethers and optionally esterifying them with an acid.