JPS5925359A - Preparation of alkylene oxide adduct of fluorine-containing compound - Google Patents

Abstract

NEW MATERIAL:An alylene oxide adduct of a compound shown by the formula I (Ar is aromatic group; Q is carbonyl, methylene, or ethylene; n is 1-3; R2' and R3' are lower alkyl, or hydroxyalkyl) or its ester. EXAMPLE:N-Polyoxyethylene-N-methyl-N-perfluorononenyloxybenzylamine. USE:A surface active agent. Showing improved ability of the reduction of surface tension, having improved chemical resistance and heat resistance. Having specific properties such as especially oil repellency, releasability, preventing action on the reattachment of oil, stabilizing action of foams, etc. PROCESS:A novel compound shown by the formula I is reacted with an alkylene oxide, and, if necessary, it is esterified with an acid to give an adduct of the compound shown by the formula I with the alkylene oxide. The compound shown by the formula I can be obtained by reacting a compound shown by the formula IIwith an amine shown by the formula III directly or in the presence of a base.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a new LL fluorine-containing compound. Historically, a novel compound obtained by the reaction of an aromatic compound containing at least one hekylyflu A-[] pen oligomer and a human 1]-1 is perfluor[
]Algylene Aisil'' (-1 added fluorine compound (J related) obtained by reacting alkenyl aryl ether with a group that has hydrophilic properties. Very useful.

1, a typical fluorine-containing water world [n [as an activator,
Perful A locarponyl full Δ wide ((', y I I 5 COF )
J> and Perflu A Rosul small nil fluoride (Get
−＋? Various derivatives using starting material v1 such as SO2F) have been reprinted4 and are useful as surfactants.
Those having 6 or more carbon atoms have extremely low yields and are also extremely expensive, so their use is limited despite their excellent properties.

Also, those using methanol and tetrafluor A [ω-■-perfluoroal]-l (H(CF2 CF2 ) n CH20H), which is developed by the te[1-nuryization of coedylene], and perfluoroiodide (Rrl, however, There are also known starting materials such as Rf having 5 or more carbon atoms, but the former has hydrogen at the end, which reduces its properties as a fluorine-containing surfactant. In the latter case, the reaction is complicated and the yield of the desired 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 difficult 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 disadvantage 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 hexafluoro[1-propene or its oligomer with an aromatic compound containing at least one human[]xyl antagonist. . Accordingly, the present invention was developed as a result of repeated research on fluorine-containing surfactants derived from perfluoroalkenyl aryl ethers.

In particular, when the alkyleneoxy 1-adducted 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 is resistant to chemical agents. Excellent strength and heat resistance. especially,
Oil repellency 11, N1 that cannot be achieved with hydrocarbon surfactants
It has special properties such as moldability, oil re-deposition prevention effect, and 1a stabilizing effect. However, there are uses such as oil repellents, NI type agents, antifogging agents, antifogging agents, flotation agents, foaming agents, foam stabilizers, degreasing detergents, etc. that utilize the properties of nitrates. The count,
Foam extinguishing valve 1, Toyuji,
Penetrant, "Fulsion breaker, Dyeing aid, Metsu: 1
It can be used in an extremely wide range of applications, such as cooling agents and emulsifiers for fluororesin emulsification. Furthermore, the perfluoroalkenylaryl I-fluors used in the present invention can be obtained in high yields as described in, for example, Patent No. 1, 1972-026959, and can be put to practical use in terms of price.

General formula used as a raw material for the fluorine-containing compound of the present invention: %Formula% [[]UIn the formula, Ar is an aromatic M group that may have a substituent, Q
is a carbonyllene group; Produce perfluoroalkenyl aryl ethers.

(Aromatic compounds that have at least one hydroxyl group here are, in principle, aromatic hydrocarbon compounds that have one or more hydroxyl groups on an aromatic nucleus such as benzene or naphthalene, and have an alkyl group as a substituent. group, aryl group,
It may have an acyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, a nitro group, a halogen group, a cyano group, a sulfone M group, or an acid amide group having no active hydrogen.

Further, the typical structure of the perfluoroalkenyl group of the perfluoroalkenyl aryl ethers obtained here is designated as having the following formula by NMR analysis.

(1) Perfluoropropenyl group: CF 3 to CF = CF - (2) Perfluorohex is a nyl group: (3) Perfluoro[1 nonenyl group: F3. ) This is then induced to compound [I11] by the following method.

(1) Perfluoroalkenyloxyaryl halides: mono- or civalides of perfluoroalkenyl aryl ether and dialkyl ether ((
XI (C)-12) mO(CH2)m+-1, or (XI (CH2>, , O)2: where m is an integer of 1 or 2, and X has the same meaning as above.

Primarily, chloromethyl methyl ether is used.

) to react.

(2) Perfluoroalkenyloxyarylcarbonyl halides: hexafluoropropene or hexafluoropropene oligomer and phenyl hydroxyarylcarboxylate (HO-Ar COOC6H5; in the formula, Ar has the same meaning as above. Mainly p- phenyl hydroxybenzoate is used) to obtain phenyl perfluoroalkenyloxyarylcarboxylate, which is then hydrolyzed and the resulting carboxylic acid is treated with dionyl halide. .

Compound [I[[] and general formula obtained by the above method; % formula %
[In the formula, R'2 and R13 each represent hydrogen, a lower alkyl group, or a hydroxyalkyl group, and at least one of them represents hydrogen or a hydroxyalkyl group. ] By reacting with amines represented by the general formula: % formula % ] In formula 1, R' 2 , R' 3 , Ar , Q and "
1 obtains the same compound shown as L1 as above. - Examples of amines include methylamine, cochylamine, propylamine, and alkanolamines, including alkylene groups with carbon atoms of 4 or less, especially monoethanolamine, jetanolamine, monopropaturamine, cyfrobanolamine, N-methyl Ethanolamine, N-ethylethanolamine, etc. are preferred. The reaction can be easily carried out directly or in the presence of a base, in an aqueous or organic solvent. Note that the alkanol amine derivative can also be obtained by reacting compound [I[1] with ammonia or a primary amine, and then reacting it with ethylene oxide, propylene oxide, or butylene oxide, etc., but the method described above is preferable. is preferable because it does not cause side reactions and the reaction time is short.

When alkanolamines are used as the compound [VT] in the present invention, the product is further reacted with an alkylene oxide to produce a polyoxyalkylene derivative. As the catalyst, it is preferable to use an alkali metal base such as sodium hydroxide or a tertiary amine, but an acid catalyst such as fluoride chloride may also be used. Generally, when using Al-7J catalyst, 100 to 200
℃, and in the case of an acid catalyst, it is preferable to react at around 100℃.

Furthermore, when ammonia or monoalkylamine is used as an amine in the synthesis of compound [VU], tyrene oxidation may be directly added thereto. In this case, it goes without saying that the above catalysts can be used. These polyoxyalkylene derivatives can also be esterified with chlorosulfonic acid, sulfuric acid, phosphorus oxychloride, phosphoric anhydride, and the like.

Hereinafter, Kikomei will be explained by giving examples.

Example 1 N-polyoxyethylene-N-methyl-N-perfluorononenyloxybenzylamine (C9FI70C6t1, C1'2N (Ctl3
) (CH2Cf” 2 0) 8.4
H) Preparation γ Removal: (1) 52.4% (0.1 mol) of p-perfluorononenylphenyl ether and 45% glacial acetic acid. Add Og (('), 75 mol), ferric chloride 24.3 (+ (0゜15T nil), 7tsuku[1] dimethyl ether 19゜/I5!J (0.22 mol), and at 70°C. The reaction is stirred for 72 hours. The end point of the reaction is confirmed by gas chromatography when the peak of 1)-perfluorononenylphenyl nityl disappears. Pour the reactant into water, separate the insoluble f1 liquid, and reduce! “It’s steaming.

56.1 g (98% yield) of a fraction (colorless transparent liquid) with a boiling point of 86.5 to 87.0'C/1.5 mm 1-10 is obtained. This fraction did not show a single peak in gas chromatography. Elemental analysis: F56.80% (calculated value 56.
39%), and the infrared absorption spectrum confirms that it is perfluorononenyloxypensyl chloride.

(2) Perfluorononenyl first obtained in (1) above
Dibenzyl chloride 'ii, 45g (0°02 mol)
and 3.80 g (0.05 mol) of N-methylethanolamine are reacted directly (with stirring at 30'C for 3 hours. The reaction product is poured into water, the insoluble liquid is separated and evaporated, and the boiling point is 129.
Take a fraction of ~132°C/2.5 mm f-1o. 11.58 g (95% yield) of a viscous liquid are obtained. Droxyethylene-N- to N- by infrared absorption spectroscopy
It is confirmed that it is methyl-N-perfluorononenyloxybenzylamine.

(3) 9.1 g (0.01 g) of the compound obtained in (2) above
When Na0l-1 was added to 5 tons of water and cooled with water for 1 hour, 4.40 (0°1 mole) of ethylene oxide was reacted in an autoclave, and the average molecule! ! N-polyoxyethylene-N-methyl-N- with 8.4 moles of ethylene oxide added
Perfluorononenyloxybenzylamine is obtained.

Example 2 N,N-bis(polyΔ1 diethylene ip-perfluor Alononenyl primary dibenzamide (C9 + ? O
C6t-L CON [(CH2CH20)e,?
H]2 manufacturing method: (1) p-perfluorononenyloxybenzoic acid 5
6.80 (0.1 mol) to thionyl chloride 35°7o (
0,3 mol) and stirred at room temperature for 1 hour.
Confirm by the disappearance of the nonenyloxybenzoic acid peak). The reaction product is poured into water, the insoluble substances are separated and distilled under reduced pressure. Boiling point 96.5 = 97.OoClo, 5mm
) -1iJ fraction (S color transparent liquid) 58.0 g is obtained (yield *99%). Elemental analysis: F55.50% (calculated value 55.05%).

Infrared absorption spectrum: C-F7.5-9.5μC-0;
5.60μ, 5.66μ. From the above results, []-paperfluorononenyloxybenzylamine is confirmed.

(2) Add 11.7o (0.02 mol) of perfluorononenylbenzoyl chloride obtained in (1) above to
~ Dissolved in 50πβ of lahydrofuran, add 4.2 (00.04 mol) of jetanolamine thereto, stir and react at room temperature for 2 hours. Distill the solvent from the reaction product,
Pour into water and add 1 to 30% chloride to salt out. When the precipitated liquid layer is dehydrated and dried, a light brown viscous liquid 11.79
(] (yield 90%). Gas chromatography and infrared absorption spectrum analysis confirmed that it was N,N-bis(hydroxyethylene)-[]-perfluorononenyloxybenzamide. Ru.

(3) Compound 13.1 (1(0,
0.02 mol) was reacted with 17.6 (+ (0.4 mol)) of ethylene oxide in the same manner as in (3) of Example 1. The reaction was completed in 160±10'C of 124 hours.

A brown waxy substance of 24.6% is obtained.The average mole number of ethylene oxide is 17.4 moles.

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 the Wilhelmi method, temperature 2
5℃, subject: glass plate). The results are shown in Table-1.

As can be seen from Table 1 below, the surface tension of the conventional hydrocarbon surfactant is 30 to 35 dyne/cn+r at 0.1% (weight/volume), whereas the fluorine-containing surfactant of the present invention In the compound, it is 30 dyne10n+.

Example 4 (Oil redeposition prevention 1 test) 0°01% of the fluorine-containing surfactant obtained in Example 1
Clean metal pieces in a degreasing solution containing (suspension/capacity) 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 to the surface, and re-deposition of oil is prevented. For hydrocarbon surfactants,
Oil removed by cleaning adheres to the metal piece again, resulting in incomplete cleaning.

Example 5 (#li type property) An aqueous solution of 1q of fluorine-containing surfactant in Example 1 containing 0.2% (car weight/easiness) is applied to a mold. Molten polystyrene is poured into this and molded. After molding, the polystyrene resin can be removed from the mold very easily.

Continuation of page 1 0 shots Mikami Taihei 7-8 Nagaimachi Higashi, Osaka 0 shots: Motoshigeru Kuma 2-34 Minamimukonosho, Amagasaki City No.13 Tachibanaso

Claims (1)

[Claims] 1. General formula: % formula % [wherein, Ar is an aromatic group, Q is a carbonyl group, methionone group, or ethylene group, [1 is an integer from 1 to 13, and I '2 and R13 are each hydrogen, a lower alkyl group, or a 1-[1-xy-alkyl group, in which at least one of them is 1 representing hydrogen or a 1-4-dialkyl group, and an alkyl oxide is reacted with the compound. A method for producing an alkylene oxide-added fluorine-containing compound, which comprises esterifying with an acid.