JPS6050779B2 - Production method of ethylene oxide-added fluorine-containing compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing an ethylene oxide-adducted fluorine-containing compound.

More specifically, a method for producing an ethylene oxide-added fluorine-containing compound obtained by reacting a hydrophilic group with a new compound perfluorononenylphenyl ether obtained by the reaction of hexafluoropropene trimer and phenol. Regarding. This compound is particularly useful as a surfactant. Conventionally, typical fluorine-containing surfactants include perfluorocarbonyl fluoride (C7F15COF) and perfluorosulfonyl fluoride (C7F15COF) obtained by electrolytic fluorination.

F,,SO. Various derivatives using starting materials such as F) are commercially available. These compounds having 6 or more carbon atoms, which are useful as surfactants, have extremely poor yields and are therefore very expensive, so their use is limited despite their excellent properties. J In addition, there are those using ω-H-perfluorocalcohol (H(CF2CF2)nCH2OH) obtained by telomerization of methanol and tetraphrheoloethylene as a starting material, and those using perfluoroiodide (R
There are also known starting materials such as fl, 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. There are drawbacks to this.

In addition, the latter reaction is complicated, and the yield of the desired product as well as the yield of the desired 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, as a result of repeated research on fluorine-containing compounds derived from perfluoroalkenyl aryl ethers, the present invention was completed. In particular, when the fluorine-containing compound based on the present invention is used as a fluorine-containing surfactant, it exhibits superior surface tension lowering ability and chemical resistance compared to pentahydrocarbon surfactants. , has excellent heat resistance.

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, and degreasing agents. Other special properties include fire extinguishing foam, oil collecting agents, penetrating agents, emulsion breakers, dyeing aids, and plating additives!
It can be expected to have an extremely wide range of applications, such as emulsifiers and emulsifiers for fluororesin emulsion polymerization. Moreover, the perfluorononenyl phenyl ether used in the present invention is, for example,
As described in No. 9-0269, it can be obtained in high yield and is reasonably priced for practical use. The compound represented by the general formula used as a raw material for the fluorine-containing compound of the present invention: [In the formula, Q represents a carbonyl group or a methylene group, and X represents chlorine or bromine] is made from a hexafluoropropene trimer and phenol. First, perfluorononenyl phenyl ethers are produced.

The typical structure of the perfluorononenyl group of the perfluorononenyl phenyl island ethers obtained here is estimated to be that of the following formula by NMR analysis.

Next, this is induced into compound [■] by the following method.

(1) Perfluorononenyloxyphenyl methylene halides: mono- or dihalides of perfluorononenyl phenyl ether and dimethyl ether (XlCH2
OCH3 or (XlCH2)20: In the formula, X1 represents a halogen. Mainly, chloromethyl methyl ether is used). (2) Perfluorononenyloxyphenylcarbonyl halides: hexafluoropropene trimer and phenyl hydroxybenzoate (
: p-hydroxybenzoate is mainly used) to obtain phenyl perfluorononenyloxybenzoate, which is then hydrolyzed and the resulting carboxylic acid is treated with thionyl halide. You can get it by twisting it.

The compound [■] obtained by the above method and the general formula: [wherein R
Amines represented by 2 and R3, each of which represents hydrogen, a lower alkyl group, or a hydroxyethyl group, at least one of which represents hydrogen or a hydroxyethyl group (except when both are hydrogen) By reacting with, the general formula: [In the formula, R゛2R゛3 and Q have the same meanings as above.

] is obtained. The amines include methylamine, ethylamine, propylamine, and the alkanolamines include alkylene groups having 4 or less carbon atoms, particularly monoethanolamine, diethanolamine, N-methylethanolamine, N-ethylethanolamine, and the like. The reaction can be easily carried out in water or an organic solvent, directly or in the presence of a base. The alkanolamine derivative can also be obtained by reacting the compound [■] with ammonia or a primary amine and then reacting with ethylene oxide, but the above method is better in that no side reactions occur and the reaction time is shorter. is preferable because it is short. In the present invention, when ethanolamines are used as the compound [■], the product is further reacted with ethylene oxide to produce a polyoxyethylene derivative.

As a catalyst, an alkali metal base such as sodium hydroxide or a tertiary amine is preferably used, but an acid catalyst such as boron fluoride may also be used. Generally, when using an alkali catalyst, the temperature is 100 to 200'C under normal pressure or increased pressure.
When using an acid catalyst, the reaction is preferably carried out at around 100°C. Furthermore, when a monoalkylamine is used as an amine in the synthesis of the compound [■], ethylene oxide may be added directly to it. In this case, it goes without saying that the above catalysts can be used. R゛2 of the compound represented by the general formula [■]
and when R゛3 is hydrogen or a hydroxyethyl group, a compound represented by the formula: [wherein Q has the same meaning as above and n indicates the average number of bonds (1 to 40) of oxyethylene groups] is obtained.

When either R'2 or R'3 is a lower alkyl group, a compound represented by the formula: [wherein Q and n have the same meanings as above and R' represents a lower alkyl group] is obtained. .

When R'2 or R'3 is hydrogen, the number of moles of ethylene oxide added is n, and when it is a hydroxyethyl group, the number of moles added is n-1. The number of moles of ethylene oxide added may be arbitrarily selected depending on the desired hydrophilicity of the obtained ethylene oxide-added fluorine-containing compound. When used as a surfactant, n is generally about 1 to 40 moles.
The addition reaction of ethylene oxide and the adjustment of the number of moles added may be carried out by a well-known method commonly used for hydrocarbon nonionic surfactants. The present invention will be explained below with reference to Examples.

Example 1 N-polyoxyethylene-N-methyl-N-perfluorononenyloxybenzylamine (C9Fl7OC8
Method for producing group CH2N(CH3)(CH2CH2O)8.4H): (1) Add 52.4y (0.1 mol) of p-barfluorononenylphenyl ether to 45.0y (a) of glacial acetic acid.
．． 75 mol), ferric chloride 24.3y (0.15 mol)
, monochlorodimethyl ether 19.45q (0.22
mol) was added, and the reaction was stirred at 70'C for several hours.

The end point of the reaction is confirmed by gas chromatography when the peak of p-perfluorononenylphenyl ether disappears. Pour the reaction product into water, separate the insoluble liquid, and distill it under reduced pressure. Boiling point 86.5-87.0°C/1.5 MoHg
A fraction (colorless transparent liquid) of 56.1V (yield 98%) was obtained. This fraction shows a single peak on gas chromatography. Elemental analysis; F; 56.80% (calculated value 5
6.39%), infrared absorption spectrum analysis; C-F; 7
．． 5-9.5μ (broad absorption), ku●)〉; 6.27μ
, 6.70μ.

From the above results, it can be confirmed that it is p-perfluorononenyloxybenzyl chloride. (2) Above, barfluorononenyloxybenzyl chloride 11.45q
(0.02 mol) and N-methylethanolamine 3.80
g (0.05 mol) was directly stirred and reacted at 60° C. for 3 hours.

The reactant is poured into water, and the insoluble liquid is fractionated and distilled to obtain a fraction with a boiling point of 129-137C/2.5TI$LHg.
11.58y of viscous liquid (yield 95%) is obtained. Infrared absorption spectrum analysis confirms that it is N-hydroxyethylene-N-methyl-N-perfluorononenyloxybenzylamine. (3) Add NaOH to the compound 9.1y (0.015 mol) obtained in (2) above.
After dehydration and cooling, 4.4y (0.1 mol) of ethylene oxide was reacted in an autoclave, resulting in an average molecular weight of 8.
．． N-polyoxyethylene-N-methyl-N-perfluorononenyloxybenzylamine to which 4 moles of ethylene oxide have been added is obtained.

It was not possible to measure the melting and boiling points of this compound.
Example 2 N,N. Bis(polyoxyethylene)-p-perfluorononenyloxybenzamide (C9Fl7OC6Hl
Manufacturing method of CON [(CH2CH2O)8.7H]2):
(1) p-perfluorononenyloxybenzoic acid 56.
8 da(a). 1 mol) of thionyl chloride 35.7q (0.
(3 mol) and stirred at room temperature for 1 hour (the end point of the reaction is confirmed by gas chromatography by the disappearance of the peak of p-perfluorononenyloxybenzoic acid).

The reaction product is poured into water, and insoluble substances are separated and distilled under reduced pressure. 58.9q (yield: 99%) of a fraction (colorless transparent liquid) with a boiling point of 96.5-97.0°C/0.5TWLHg is obtained. Elemental analysis: F: 55.50% (calculated value 55.05%
), infrared absorption spectrum analysis; C-F; 7.5-9.
5μ (broad absorption), 6.27μ, 6
．． 70pNC=O; 5.60μ, 5,66μ. p-perfluorononenyloxybenzoyl chloride can be confirmed from the above crystals. (2) Above perfluorononenyloxybenzoyl chloride 11.7y (0.02 mol)
was dissolved in 50TrL1 of tetrahydrofuran, and 4.2f1 (0.04 mol) of diethanolamine was added thereto.
The reaction is stirred at room temperature for 2 hours. The solvent is distilled off from the reaction mixture, poured into water, and sodium chloride is added for salting out. When the precipitated liquid layer is dehydrated and dried, it becomes a pale brown viscous liquid11.
79y (yield 90%) is obtained. Gas chromatography and infrared absorption spectroscopy revealed that N,N-bis(
It is confirmed to be hydroxyethylene)-p-perfluorononenyloxybenzamide. (3) Compound 13.1y(a) obtained in (2) above. 02 moles)
In the same manner as in Example 1 (3), ethylene oxide 17.6
q (0.4 mol) is reacted.

The reaction was completed in 124 hours at a reaction temperature of 160±10°C. 24.6 q of brown waxy material are obtained. The average number of moles of ethylene oxide added is 17.4 moles. Although the melting point and boiling point of the obtained compound could not be measured, its surface tension was as shown in Table 1. Example 3 Each surface tension was measured by changing the concentration of the fluorine-containing compound obtained in Example 2 above (measurement was performed using Wilhelmian method, temperature 2
5゜C1 target: glass plate).

The results are shown in Table-1. As can be seen from the table above, the surface tension of conventional hydrocarbon surfactants is 0.1
% (weight/volume), at most 30 to 35 dyne/C
m, whereas in the fluorine-containing compound of the present invention, it is 30c1
It is yne/o.

Claims (1)

[Claims] 1. General formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼[VII] [In the formula, Q
is a carbonyl group or a methylene group, and R'_2 and R'_3 are each hydrogen, a lower alkyl group, or a hydroxyethyl group, and at least one of them is hydrogen or a hydroxyethyl group (except when both are hydrogen) A formula characterized by reacting a compound with ethylene oxide: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, Q has the same meaning as above, R ' represents a lower alkyl group and n represents the average number of bonds (1 to 40) of oxyethylene groups.