JPS5925358A - Preparation of fluorine-containing amino compound - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula I (Ar is aromatic group; Q is carbonyl, methylene, or ethylene; R2' and R3' are H, lower alkyl, or hydroxyalkyl; n is 1-3) and its ester. EXAMPLE:N-Hydroxyethylene-N-methyl-perfluorononenyloxybenzylamine. USE:A surface active agent. Showing improved ability on the reduction of surface tension, having improved chemical resistance, and heat resistance. Having specific properties such as oil repellency, releasability, preventing action on the reattachment of oil, stabilizing action on foams, etc. PROCESS:A compound shown by the formula II (X is Cl or Br) is reacted with a compound shown by the formula III to give a compound shown by the formula I , and, if necessary, it is esterified with an acid to give the desired fluorine-containing amino compound. The reaction can be carried out directly or in the presence of a base in water or an organic solvent easily.

Description

[Detailed description of the invention] The present invention relates to a new fluorine-containing amine compound.

More specifically, a novel compound obtained by the reaction of a heglyfluoropropene oligomer and an aromatic compound having at least one human 1]oxy group, perfluor, jr] flukenyl aryl ether, has hydrophilic properties. Zu-
The present invention relates to a method for producing a hydrous compound obtained by avoiding the reaction of 1<. This compound is especially Ishikawa as a surfactant.

Conventionally, typical fluorine-containing surfactants include perfluorocarbonyl fluoride 1 (07 F+ 50OF) and perfluorosulfonyl fluoride (CBF+ 7802 F) obtained by electrolytic fluorination.
Various derivatives are commercially available using starting materials such as surfactants, but those with 6 or more carbon atoms, which are useful as surfactants, have extremely poor yields and are therefore very expensive.
Despite its excellent properties, its use is limited.

Also, tn -1-1-perfluoroalcohol <+-1(CF2 CF2 > n CH20'H) obtained by telomerization of methanol and tetrafluoroethylene
) and perfluoroiodide (
There are also known starting materials such as Rf I (where R has 5 or more carbon atoms), but the former has hydrogen at the end, so its properties as a fluorine-containing surfactant are reduced. The latter also has the disadvantage that 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 methods that use tetrafluoroethylene oligomer as the 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 of the oligomer is adjusted to 99, it is difficult to handle.
Since a wax-like polymer with a polymerization degree of 1 to 1 is produced in comparison, there is a drawback that the conversion rate of an oligomer having a carbon number useful as a surfactant is poor.

The present inventors previously reported that hexInafluoro[17F] pen or other oligomers and at least one hydroxyl group
The reaction with aromatic compounds having more than 4 τ(1, \-fluoroalkenyl aryl ether l)\ et al. As a result of repeated ωI research on fluorine-containing compounds, the present invention was completed.

In particular, when a fluorine-containing compound based on wood and light is used as a fluorine-containing field i'ri'I activator, charcoal,
% compared to basic surfactants, it exhibits excellent surface tension lowering ability, and has improved chemical resistance and heat resistance. (1 old oily, f
It has special properties such as antibacterial properties, IV re-adhesion prevention effect, and foam stabilizing effect. These properties are used in oil repellents, mold release agents, antifouling agents, antifogging agents, flotation agents, foaming agents, foam stabilizers, degreasing agents, and other products.

In addition, an extremely wide range of applications can be expected as products that utilize special properties, such as foam extinguishing agents, oil collection agents, penetrants, emulsion breaker-1 dye negative auxiliaries, plating additives, and emulsifiers for fluororesin emulsion polymerization. It is. Moreover, the perfluoroalkenyl aryl ethers used in the present invention can be obtained in high yields as described in, for example, Japanese Patent Application No. 1983-026959, and can be put to practical use in terms of price.

The present invention has the general formula: % formula %[111] [wherein, X is chlorine or bromine, Ar is an aromatic group, Q is a carbonyl group, methylene group or ethylene group, and n is 1 to 3
an integer of ] A compound represented by the general formula: % formula % [[wherein R' 2 and R' 3 each represent hydrogen, a lower argyl group, or a hydroxyalkyl group, -d-] is reacted. General formula characterized by: % formula %] In the formula 1, Ar , Q, R' 2, R' 3J9 and n have the same meanings as above.] and optionally J: The present invention relates to a method for producing a fluorine-containing amine compound by esterifying the compound with an acid.

The compound represented by the general formula used as a raw material for the fluorine-containing amine compound of the present invention; First, a perfluoroalkenyl aryl ether is produced from the compound and an aromatic compound '''A having at least one or more hydroxyl groups.

(Aromatic compounds having at least 1 J group of hydroxy groups herein are, in principle, aromatic hydrocarbon compounds having one or more hydroxy groups on an aromatic nucleus such as benzene, naphthalene, etc., and as a substituent, an alkyl group, aryl group,
Acyl group, alkoxy group, -! It may have a carboxyl group, an alkoxycarbonyl group, a nitro group, a halogen group, a cyan group, a sulfonic acid group, or an acid amide group having no active hydrogen.

In addition, the typical groove 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 group: CF3-CF=CF- (2) Perfluorohexenyl group: (3) Perfluorononenyl group: This is then converted into a compound "■" (this derivative J) by the following method.

(1) Perfluoroalkenyloxyarylargylene halides: perfluoroalkenylaryl ■-thyl and dialkyl ether mono- or cybalides ((
XI (CI-12) lnO(C112) mHl or (XI (CI-12>mO> 2 : where,
■ 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: hexylifluorobropene or hexylifluoropropene oligomer and phenyl hydroxyarylcarboxylate < 1-(0-A r -COOC6
I-15; In the formula, ha 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.

By reacting the above compound [Ir1l with a compound represented by the general formula: %Formula% [wherein R'2 and .R'3 have the same meanings as above], the general formula: %Formula% [ ] [Formula Middle, R'2, R'3, Ar, and Qonibi n have the same meanings as above. In order to obtain the compound represented by , methylamine, ethylamine, propylamine, dimethylamine, dimethylamine, methyledylamine and other lower dialkylamines can be used. As the alkanolamines, alkylene groups having carbon atoms of 4 or less are preferred, particularly monoethanolamine, jetanolamine, monopropaturamine, dibrobanolamine, N-methylethanolamine, and N-ethylethanolamine. 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 [111 with ammonia J, a primary amine, etc., ethylene oxide, propylene oxide, butylene oxide, etc., but the method described above is preferable. It is remarkable because it does not cause side reactions and the reaction time is short. If necessary, these alkanolamines can be reacted with chlorsulfonic acid, sulfuric acid, Δ:1 dichlororicillin hydrophosphoric acid, etc. to obtain their (sales acid esters or phosphoric esters). It can also be neutralized with an unrelated base to form various salts.

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

Example 1 Process for producing N-hydroxyethylene-N-methyl perfluorononenyloxybenzylamine: (1) Process for producing p-purple olononenyloxybenzyl chloride: p-perfluorononenyl phenyl ether 52.4 (
1 (0.1 mole), glacial acetic acid 45.0 (1 (0.75 mole), ferric chloride 24', 3 g (0.15 mole), monochlorodimethyl ether 19.45 g (0.22 mole)
The mixture was stirred and reacted at 70°C for 72 hours. The end point of the reaction is confirmed by gas chromatography when the peak of p-perfluorononenylphenyl ether disappears. The reactant is poured into water, the insoluble liquid is separated and distilled under reduced pressure. Boiling point 86.5-87. ．． O℃/1,5mmHo
(1) Distillate (colorless transparent liquid) 56.1g (yield 98%)
) is obtained. This fraction shows a single peak on gas chromatography. Elemental analysis: F1a, 80% (calculated value 56.39%), infrared absorption spectrum analysis; 27μ,
6.701z, from the 20 Shao-Sung Dynasty, it is certain that it is p-perfurunrononenyl A-gyshibenzyl chloride.

11.45 CI (0.02 mol) of perfluorononenyl chloride and N-
Methylethanolamine 3. '80 (+ (0.05
mol) were directly reacted at 60'C for 3 hours and 10 minutes.

The reactant was injected into water, the insoluble liquid was fractionated and collected, and the boiling point was 129-132°C/2. Take a fraction of 5 mml-1o.

A viscous liquid 11.58 (1 (yield 95%) is produced (!1.
] Is it true that it is ethylene-N-methyl-N-perfluorononenyloxybenzylamine? be done.

Example 2 N. Method for producing N-bis(hydroxyedylene)-p-perfluorononenyloxybenzamide: (1) p-
Pernol-cononenyloxybenzoyl chloride!
FJi accused: p-perfluorononenyloxybenzoic acid 56.

8(+ ('0.1 mol) to thionyl chloride 35.7C
Add I (0.3 mol) and stir at room temperature for 1 hour (the end 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. Boiling point 96.5-97, 0°C 10. 5n+ml-
A fraction of 1 cI (colorless transparent liquid) 58, OOh< is obtained (yield 09%). Elemental analysis; F55.50% (IT calculated value 55.(')5%). Infrared absorption spectrum: C-F7
．． 5 to 9.5μ (wide range of 5, 60μ, 5.66μ). From the above results, p-perfluor A'lononenyloxybenzoyl chloride is confirmed.

(2) Dissolve the above perfluorononenylbenediyl chloride 11.7 (1 (0.02 mol) in tetrahydrofuran 50πβ), and add jetanolamine 4.2 (1 (0.04 mol) to this). ) and
Stir and react in a room for 2 hours. The solvent was distilled off from the reaction mixture, poured into water, and 1-lium chloride was added thereto, followed by stirring. When the precipitated liquid layer is dried with In2 water, a pale brown viscous liquid 11,790 (yield 90%) is obtained. From gas chromatography and infrared absorption spectrum analysis, N. 1.TI is N-bis(hydroxyethylene perfluorononenyl oxybenzamide)
I can recognize it.

Example 3 N-(p-perflu Alononenyl A xybenzyl)-N
, N-Dimethylamine production method: p-perfluorononenylogishibenzilk synthesized in the same manner as in Example (1) [colide 10.3 <0.018 mol] was added with a dimethylamine aqueous solution (40%>) 8.74] and stir the reaction at room temperature for 2 hours. The end point of the reaction is determined by the disappearance of the peak of p-perfluorononenylonyredibenzyl chloride in Gas Chroma 1-Graphie. Place the substance in water (), separate the insoluble colored liquid layer, and distill it under reduced pressure.

Boiling point 90-90.5℃/1.5 mml-l g
fraction (pale yellow liquid) 10.35 (1 (yield 99
%) is obtained. This fraction showed a single peak in gas chromatography, and as a result of infrared absorption spectroscopy, N-<p-perfluorononenyloxybenzyl)-
'N,N-dimedylamine can be confirmed.

Continuation of page 1 0 shots Akira Motoshigeru Kuma 2-34 Minamimukonosho, Amagasaki City No. 13 Tachibana Dormitory

Claims (1)

[Claims] 1. General formula: % formula % [] [In the formula, X is chlorine or bromine, Ar is an aromatic group, Q is carbonyl, and n is an integer of 1 to 3. ] A compound represented by the general formula: %Formula% [] [In the formula, R'2 and R'3 each represent hydrogen, a lower alkyl group, or a hydroxyalkyl group. ] [In the formula, Ar, Q, R' 2 , R'3; J-3
Yopin has the same meaning as forward bend. Indicated by 1. and a method for producing a fluorine-containing amine compound, which optionally esterifies it with an acid.