JPS6020374B2 - Method for producing fluorine-containing compounds - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a quaternary ammonium salt of N-(p-perfluorononenyloxybenzyl)-N,N-dialkylamine or betaine.

This compound is particularly useful as a surfactant. Conventionally,
A typical fluorine-containing surfactant is perfluorocarbonyl fluoride (C
Various derivatives using starting materials such as 7F, 5COF) and perfluorosulfonyl fluoride (C8F, 7S02F) are commercially available, but the yields of these compounds with 6 or more carbon atoms, which are useful as surfactants, are extremely low. Despite its excellent properties, its use is limited because it has poor performance and is therefore very expensive.

In addition, there are those using Yamaichi H-barfluoroalcohol (CF2CF2)nCH20H, which is obtained by telomerization of methanol and tetrafluoroethylene, as a starting material, and perfluoroiodide (Rfl, where Rf is a carbon number of 5 or more). There are also known products that use fluorine-containing surfactants as starting materials, but the former has a disadvantage in that its properties as a fluorine-containing surfactant are reduced because it has hydrogen at its terminal.

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 methods that use tetrafluoroethylene oligomers as a starting material, but this method is difficult to handle because the raw material, tetrafluoroethylene, is extremely easy to polymerize, and the oligomers still have low polymerization even if the degree of polymerization is adjusted. The present inventors have previously discovered that the yield of oligomers with a carbon number useful as a surfactant is low because some of the oligomers are produced in the form of wax-like substances with a relatively high molecular weight. Ben or its oligomer and at least one hydroxyl group
The present invention has been made in which perfluoroalkenyl aryl ethers can be obtained in good yield by reaction with an aromatic compound having at least one aromatic compound.

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 according to the present invention is used as a surfactant, it exhibits superior surface tension lowering ability compared to hydrocarbon surfactants, and has excellent chemical resistance and heat resistance. ing.

In particular, it has special properties that cannot be obtained with hydrocarbon surfactants, such as oil repellency, moldability, 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, superfoaming agents, foam stabilizers, degreasing detergents, and the like. In addition, products that utilize special properties include fire extinguishing foam, oil collectors, penetrants, emulsion breakers, dyeing aids, plating additives,
It can be expected to have an extremely wide range of uses, such as emulsifiers for fluororesin emulsion polymerization. Moreover, the perfluorononenylphenyl ether used in the present invention can be obtained with high efficiency and can be put to practical use in terms of price, as described in, for example, Tokuiso Sho 491026959. The present invention
Reacting a compound represented by the general formula: [In the formula, R'2 and R3 represent a lower alkyl group] and a compound represented by the formula: RX [In the formula, R represents a lower alkyl group and X represents a halogen]. A formula characterized by: [wherein R, R'2, R'
A method for producing a quaternary ammonium salt represented by the following formula: [3 and - Formula characterized by reacting with propiolactone: [wherein R'2 and R
'3 has the same meaning as above, q represents an integer of 0 or 1]
This invention relates to a method for producing betaine represented by

The compound represented by the formula [skin'] of the present invention is a compound represented by the formula: [wherein,
x is chlorine or bromine] and a secondary amine represented by the general formula: [wherein R'2 and R'3 represent a lower alkyl group].

The formula [m
In the compound represented by '], perfluorononenylphenyl ethers are first produced from hexafluoroprobene trimer and phenol.

The typical structure of the perfluorononenyl group of the perfluorononenyl phenyl ethers obtained here is estimated to be that of the following formula by NM ash analysis. Next, this is induced into compound [m'] by the following method.

[1] Perfluorononenyl oxyphenyl methylene halides: Mono- or dihalides of perfluorononenyl phenyl ether and dimethyl ether (X, CH2
0C ratio or (XICH2)20: where X represents halogen.

Mainly, chloromethyl ether is used). By reacting the above compound [m'] with a dialkylamine represented by the general formula: [In the formula, R'2 and R'3 have the same meanings as above], the general formula: [In the formula, R'2, R'3 has the same meaning as above.

In order to obtain the N-(p-perfluoro/nenyloxybenzyl)-N,N-dialkylamine represented by Dimethylamine, diethylamine, methylethylamine and other lower dialkylamines are preferred. The obtained compound [skin'] is further converted into a quaternary ammonium salt or betainate by conventional means.

For quaternary ammonium chloride, lower alkyl halides such as methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, and ethyl iodide are used. Betination is carried out by reacting halocarboxylic acids or 8-propiolactone to form a betaine type derivative.

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

Example 1 N-(p-perfluorononenyloxybenzyl)-N
,N,N-trimethylammonium iodide (C
9F, 70C 6 days 4C ratio N (C ratio) 31-), Nachibini betaine ((C9F, 70C 6 days 4CH 2N ten (CH3
)2・CQCOO- and C9F, 70C6AC day 2N
Production method of 10 (C is) 2 CQC day 2COO-): mp-
Production method of perfluorononenyloxybenzyl chloride: p-perfluorononenyl phenyl ether 52.4
glacial acetic acid (0.1 mol) and 45.0 ml (0.75 mol)
, add 24.3 moles (0.15 moles) of ferric chloride and 19.45 moles (0.22 moles) of monochlorodimethyl ether;
70q○ causes a 7-year-old foundation Azusa reaction.

The end point of the reaction is confirmed by gas chromatography when the peak of p-perfluorononenylphenyl ether disappears. The reaction product is poured into water, and the non-falling liquid is collected and distilled under reduced pressure. Boiling point 86.5-87.0qo/1.5 side Hg
56.1 ml of fraction (colorless transparent liquid) (yield 98%) was obtained. This fraction shows a single peak in gas chromatography. Elemental analysis; F: 56.80% (calculated value 5
6.39%), infrared absorption spectrum analysis; C-F: 7
．． 5-9. Tsubo (broad absorption): 6.27 Buddha, 6.70 Buddha.

From the above results, it can be confirmed that it is P-perfluorononenyloxybenzyl chloride. [21N-(p-perfluorononenyloxybenzyl)-N,N-dimethylamine and its quaternary ammonium salt and method for producing betaine: p-perfluorononenyloxybenzyl chloride synthesized in [1] 10.3 Evening (0.
0.018 mol) was added with 87 g of an aqueous dimethylamine solution (40%) and allowed to react at room temperature for 2 hours. The end point of the reaction is
This is confirmed by gas chromatography when the p-fluorononenyloxybenzyl chloride peak disappears. The reactant is poured into water, and the insoluble liquid layer is separated and distilled under reduced pressure. Boiling point 90-90.5℃/1.5 side Hg fraction (
10.35 ml of pale yellow liquid (yield 99%) are obtained.
This fraction showed a single peak in gas chromatography, and as a result of infrared absorption spectrum analysis, it was confirmed that it was N-(p-perfluorononenyloxybenzyl)-N,N-dimethylamine. This product 87 minutes (
0.015 mol) and methyl iodide2. Shigeyu (0.020
When the mixture is reacted dropwise with mol) at 5° C. or below and recrystallized with methanol, a pale yellow powder of 10.6% (yield: %) is obtained. By infrared absorption spectrum analysis, N-(p
-perfluorononenyloxybenzyl)-N,N,N
-trimethylammonium iodide. Although this product dissolves only in a small amount in water, it dissolves well in a water-isopropyl alcohol (2:1) mixture and exhibits good foaming properties. 90 to 95 qo of the above N-(p-perfluorononenyloxybenzyl)-N,N-dimethylamine (0.02 mol) and 3.5 qo (0.03 mol) of sodium monochloroacetate were added. After the reaction, a slightly hygroscopic pale yellow solid (12.2% yield) was obtained by extraction with ether. Infrared absorption spectroscopy revealed that N-(p-perfluorononenyloxybenzyl)- It is confirmed to be N,N-dimethylbetaine.

NMR analysis of the obtained compound was as follows.

a 7.27 leg (2H) b 7,9 Sakaki m (2H) C 5.09 pm (2H) d 4, Misaki leg e 3-4 ■ Blood (phrase H) Above, N-(p-perfluorononenyl 11.6 moles (0.02 mol) of N,N-dimethylamine (oxypenzyl) were dissolved in 50 molar diethyl ether, 2.16 moles (0.03 mole) of 8-propiolactone were added, and the mixture was heated under reflux. Allow to react for 6 hours.

The end point of the reaction is confirmed by gas chromatography when N-(p-perfluorononenyloxybenzyl)-N,N-dimethylamine disappears. The precipitate was separated by filtration and recrystallized with ethanol to obtain 12.15 kg of pale yellow solid (yield: 93%). Infrared absorption spectrum shows that N-(p-perfluorononenyloxybenzyl)-N,N
It can be confirmed that it is -dimethyl-carboxycetylammonium betaine. NMR analysis of the obtained compound was as follows.

a 7,07 legs (2H) b 7, Misaki leg C 4.5 upright plate (spot) d, 3.02 wind (thin) e 3.6$ blood (wide) f 2.81 leg (2H) Below, Examples regarding the general properties and special performance of the fluorine-containing compound obtained by the present invention will be given below.

Example 2 Using N-(p-/f-fluorononenyloxybenzyl)-N,N-dimethylbetaine obtained in (2) of Example 1, a foaming power test was conducted using the Roth-Miles method.

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. Table -
1 In the table, A represents a perfluorononenyloxyphenyl group.

Example 3 Using the fluorine-containing surfactant used in Example 2, the penetrating power was measured by the campus disk method (concentration 0.1%, temperature 2y0).

The results are shown in Table-2. Table 2 In the table, A has the same meaning as above.

Example 4 Each surface tension was measured by changing the concentration of the fluorine-containing surfactant obtained in the above example (measurement was performed using Wilhelmy method, temperature 2500, target glass plate).

The results are shown in Table-3. Table-3 In the table, A has the same meaning as above.

As can be seen from the above table, fluorine-containing surfactants have foaming properties comparable to those of conventional hydrocarbon surfactants, but are characterized by good foam persistence.

The penetrating power is also approximately the same as that of conventional surfactants. Regarding surface tension, conventional hydrocarbon surfactants are 0.1%
(polymerization/capacity) is at most 30 to 3&yne/skin, whereas the fluorine-containing surfactant of the present invention has a yn of 3
It is less than or equal to e/g. Example 5 (Oil repellency test) 0.1% (polymerization/volume) of the fluorine-containing surfactant obtained in Example 1
Cotton is soaked in the aqueous solution, dried at 120°C for 3 minutes, and Nujol oil drops are placed on top of it.

It does not penetrate oil droplets even after 2 anchor hours.

Such oiliness is a characteristic that is not seen at all in hydrocarbon surfactants. Example 6 (Oil redeposition prevention test) 0.01% of the fluorine-containing surfactant obtained in Example 1 (
The metal pieces are cleaned in a degreasing solution containing (polymerization/capacity) and contaminated oil.

Claims (1)

[Claims] 1 General formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R'_2 and R'_3 represent a lower alkyl group] A compound represented by the formula: RX [In the formula, R is a lower alkyl group and A method for producing a quaternary ammonium salt represented by the same definition as above]. 2 General formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R'_2 and R'_3 represent lower alkyl groups] A compound represented by the formula and halocarboxylic acids or β
- Formulas characterized by reacting with propiolactone: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R'_2 and R'_3 have the same meanings as above, q
represents an integer of 0 or 1] A method for producing betaine.