JPS62103041A - Fluorine-containing carboxylic acid and salt thereof - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (Rf represents perfluoroalkenyl; n is >=3) and salt thereof. USE:Raw material for surfactants and water and oil repellents. PREPARATION:A fluorine-containing alcohol expressed by formula II is reacted in an organic solvent selected from acetone, t-butyl alcohol, pyridine, chloroform and isooctane using an oxidizing agent (example; chromic acid or potassium permanganate) at <=room temperature (preferably -10-0 deg.C) to obtain a compound expressed by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a novel fluorine-containing carboxylic acid or a salt thereof useful as a raw material for a surfactant or a water/oil repellent agent, and a method for producing the same.

Problems to be Solved by the Prior Art and the Invention Carboxylic acid salts having perfluorocarbon chains are not only useful as surfactants, but also attract attention as raw materials for water and oil repellents. A lot of research has been done.

The present invention was made in order to provide a novel fluorine-containing carboxylic acid salt useful as a raw material for surfactants and water and oil repellents.

A means for solving the problems, that is, the present invention, is represented by the general formula (I): RfO(CHz)ncOOH(I) (wherein, Rf represents a perfluoroalkenyl group, and n represents a number of 3 or more). The present invention relates to a fluorine-containing carboxylic acid or a salt thereof.

The fluorine-containing carboxylic acid represented by the general formula (I) or its salt is, for example, the general formula (II): RfO(CH,)n
CH,OH(n) (wherein, Rf represents a perfluoroalkenyl group, and n
represents a number of 3 or more) in an organic solvent with an oxidizing agent to prepare the corresponding fluorinated carboxylic acid, and if desired, convert it into a salt according to a conventional method. You can get it.

In this case, the six solvents are ketones such as acetone, t-
Examples include butyl alcohol, pyridine, carbon tetrachloride, chloroform, dichloromethane, isooctane, acetic acid, acetic anhydride, etc. Oxidizing agents include chromium compounds such as chromic acid or chromium trioxide, manganese compounds such as potassium permanganate, Examples include lead compounds such as lead acetate, and halogen compounds such as periodic acid (oxygen oxidation using a catalyst such as platinum may also be used).

A particularly preferred solvent is acetone, and particularly preferred oxidizing agents are chromic acid and potassium permanganate.

The amount of the oxidizing agent to be used is not particularly limited, but in the case of chromium trioxide, for example, 2 equivalents or more is used per 1 equivalent of the fluorine-containing alcohol represented by formula (I1).

The oxidation reaction is usually carried out under normal pressure and at a temperature below room temperature, preferably at 0°C to 0°C.

The obtained fluorine-containing carboxylic acid may be appropriately neutralized with an alkali, if desired. These alkalis are not limited and may be selected depending on the purpose. The neutralization reaction may be carried out by conventional means, such as adding and mixing the above-mentioned carboxylic acid into an aqueous alkali solution, aqueous dispersion, lower alcohol solution, or dispersion, or reverse neutralization. The type of salt is not limited, but for example, alkali metals (e.g. sodium,
salts of other metals or their oxides (e.g. zinc, tin, aluminum, zirconium or zirconyl, ditanyl salts, etc.), ammonium salts,
Examples include various amine salts, alkanolamine salts, alkylalkanolamine salts, and the like.

The above-mentioned fluorine-containing alcohol is, for example, a perfluoroalkene represented by the general formula (): % formula % () (in the formula, Rf represents a perfluoroalkenyl group) and a perfluoroalkene represented by the general formula (): % formula % () (in the formula , n represents a number of 3 or more) It can be prepared by reacting an alkylene glycol in a non-aqueous solvent in the presence of a basic catalyst.

The basic catalyst is a water-soluble catalyst that promotes the dehydrofluorination reaction and absorbs the generated hydrogen fluoride. Preferred catalysts include triethylamine, trimethylamine, potassium carbonate, sodium carbonate, and the like.

The amount of the basic catalyst to be used is not particularly limited, but it is usually used in an amount of 2 to 1 equivalent, preferably approximately the same amount, relative to the perfluoroalkene.

Examples of the non-aqueous solvent include acetonitrile, N,N-dimethylformamide, tetrahydrofuran, diglyme, tetrahydropyran, dimethylcarpitol, diethyl ether, etc., with acetonitrile, N,N-dimethylformamide and tetrahydrofuran being particularly preferred.

Examples of perfluoroalkenes include tetrafluoroethylene, hexafluoropropene, and oligomers thereof.

Tetrafluoroethylene oligomer (e.g. 2m20
oligomers) are generally obtained as a mixture of a plurality of oligomers, and because separation and purification based on the degree of polymerization is difficult, they are used as a mixture.

Hexafluoropropene oligomers are mainly 2m4
These oligomers are the preferred perfluoroalkenes in the present invention.

Examples of the alkylene glycol include alkylene glycols having 4 or more carbon atoms, such as butylene glycol, pentylene gelicol, hexylene glycol, octylene glycol, decene glycol, and the like. Preferred alkylene glycols have 4 to 20 carbon atoms, more preferably 4 to IO carbon atoms. Glycols having less than 4 carbon atoms, such as ethylene glycol and propylene glycol, mainly yield cyclized products.

The reaction ratio between perfluoroalkene and alkylene glycol is not particularly limited, but usually 2 or more equivalents, preferably 2 to 3 equivalents, of the latter are used per 1 equivalent of the former to produce a fluorinated alcohol in high yield. 11fO(Ctit)nc HtOl that can be obtained and is difficult to separate
The formation of 1f (wherein Rf and n have the same meanings as above) is suppressed (excess alkanediol can be easily removed from the system by washing with water).

The reaction is usually carried out under normal pressure and at a temperature below room temperature, preferably at θ°C.
Perform at ~25°C.

Examples of fluorine-containing alcohols used as raw materials of the present invention and their physical properties are as follows.

CIIF++0(CHt)sCHCHt-1b, 9 8
8.0℃/2.5mn+lIg Colorless transparent liquid C, F, 70(CH,)ffc) [20Hb, 9 6
9-71℃/1mm11g Colorless and transparent, liquid C
s F l? O(CHt) 4CHy OHb, p
tog ~109℃/4mm11g Colorless transparent liquid CsF+tO(CHz)scHtOH b,9 106~b C9F,yO(CHt)scHtOH b,p 114~115℃10.12mlIll1g
Colorless Transparent Liquid The present invention will be explained below with reference to Examples.

Example 1 (I) Synthesis of CeF, 70(CI-1t)6CI-1tOH: A flask equipped with a stirrer, a thermometer, a reflux condenser and a dropping funnel (1OQOi) (N,N-dimethylformamide (reagent- Hexafluoropropene trimer (
0.5 mol of a mixture of three types of isomers) was gradually added dropwise, and after the addition was completed, stirring was continued for about 8 hours.

The reaction mixture was thoroughly washed with a dilute aqueous hydrochloric acid solution, then repeatedly washed with water, dried over anhydrous magnesium sulfate, and distilled under reduced pressure to give a colorless transparent liquid (I06-1
10° C./4 mmHg) 1 3 0.79 was obtained. The gas chromatography purity of this fraction was 90% [Detector: FID, column (stainless steel), length: 1 m,
Packing material: 5E-30, carrier gas 2N7, injection temperature: 190°C, column temperature = 140°C, holding time = 1,64 min] IR and ' of the product
H-NMR data is shown below.

Infrared absorption spectrum Absorption based on OH group...3600-3100cm
- Absorption based on direct C11 group - 2944. 287
Absorption based on 2cm''IC=C - 1614cm
-'Absorption based on CF group = 1360~l100c
m'* 2, 0 5 (singlct, 1103, 5
5 ([riplet, 2 1-1) 3, 8
6 (triplet, 2l-1)loft%C C
U4 solution*: Disappeared by addition of D20 (2) Synthesis of CeF 170(C1lz)5cOOH:
- a flask (I000″l) equipped with an apparatus similar to (I)
l12) with potassium permanganate treated acetone 20
0xQ was added, and while cooling the flask to below -5°C in an acetone water bath, 0.1 mol of the fluorinated alcohol prepared in (I) and Jones reagent 551 (2) were simultaneously slowly added dropwise, and the color of the reaction solution was adjusted. After 2g of water stopped changing, the reaction mixture was extracted with chloroform, dehydrated with anhydrous magnesium sulfate, concentrated, and distilled under reduced pressure to form a colorless transparent liquid (I03℃~IO6℃10 .15m
mHg) 37.99 was obtained.

The gas chromatography purity of this fraction was 85% [Detector: FID, column (stainless steel): length;
1ml filler; Thermon-3000, carrier gas: Nt, injection temperature: 200°C,
Column temperature: 150°C, retention time: 3.95w1n]
.

The IR and 'I-1-1-N data for the product are shown below.

Infrared absorption spectrum - Absorption based on 011 and C-11 groups: 3600-2
Absorption based on -C=O group + 171
9cm-'Absorption based on C=C group: l617c shoulder-
Absorption based on 1-CF group: 1380-1100c
m-'' I-[-N M r1 analysis (δppm, internal standard TMS) 1, 50 (multiplet
61-1) 2, 27 Qriplet 21-1
)3,90 (triplet 2 ID11
, 86 (singlet l H) 10wt%CC
C, Solution Example 2 (I) Synthesis of CsF++0(CH*)scHtOH; 1 equipped with a stirrer, thermometer, reflux condenser and dropping funnel
ooOi (commercial reagent-grade in 7 flasks!

6-hexanediol (0,50 mol), triethylamine (0,250 mol) and acetonitrile 10
0yt (l) and while cooling the flask to a water-water temperature dust, add 1Xo, 25 mo of perfluoro-2-methyl-2-pentene (hexafluoropropene dimer).
l) was gradually added dropwise. After completion of the dropwise addition, stirring was continued for about 8 hours. After completion of the reaction, the mixture was thoroughly washed with a dilute aqueous hydrochloric acid solution, and after repeated washing with water, the oil was dried over anhydrous magnesium sulfate. The yield of the target alcohol was 71% based on the gas chromatography area ratio. On the other hand, the amount of a by-product, a compound whose both ends were blocked with perfluoroalkenyl groups, could be kept to 8%. The dried oil was subjected to fractional distillation to obtain the desired compound having a boiling point of 88.0°C/2 and 5 mmHg. The fraction was subjected to gas chromatography under the following conditions, and it was confirmed that it showed a single peak.

Gas chromatography conditions Detector: FID Column (stainless steel): Length 1m, packing material 5E-30
Carrier gas: N.

Injection i+u degree: l 70℃ expansion degree
: 120℃ Chart feeding speed : 20mm/min Holding time : 2.2 minutes Appearance : Colorless transparent liquid (room temperature) Infrared absorption spectrum Based on group 01-1 Absorption -3650,3325cm-
'Absorption based on CH group -2947,2865cm-'C
=Absorption based on C...1633 cm-'Absorption based on CF group-1400~l100cm-''H-N
MR analysis (δppm, internal standard substance 11MDS) 1
．． 41 (lultiplet 8H) 3, 50
(tripIet 2 N) 4 , 22 ([ri
plet 2 II) 4, 46 (singlet
I H) (2) CsF, 0 (Ctlt) scOOI
- Synthesis of [: flask equipped with equipment similar to (I) (I
000! Add 200 yt (l) of acetone treated with potassium permanganate to &), and while cooling the flask to below 15°C in an acetone water bath, add 0.1 mol of fluorine-containing alcohol prepared in (+) and Jones test 155x&. At the same time, the reaction mixture was gradually added dropwise and after the color of the reaction solution did not change, 2Q of water was added, and the reaction mixture was extracted with chloroform, dehydrated using anhydrous magnesium sulfate, concentrated, and subjected to vacuum distillation. Colorless transparent liquid (I3℃~117℃/2mm
r1g) 37.99 was obtained. The gas chromatography purity of this fraction was 85% [Detector: FID, column (stainless steel); length: 1 m, packing material; Ther
mon -3000, carrier gas diN2, temperature = 200°C, column temperature = 150°C,
Berth maintenance time: 3.30m1n].

IR and 'H-NMR data of the product are shown below.

Infrared absorption spectrum Absorption based on 011 group and C-1: 3600~
2400cI11-' Absorption based on C=O group: 1
716cm-' Absorption based on C-C group: 1638c
Absorption based on m-'C-F group: 1400-1100
cm-''H-NMR analysis (δppm, internal standard T
MS) 1, 57 (multiplet, 6H
) 2.30 (triplet, 2H) 4, 20 (triplet, 2H) 11, 8
0 (singlet, IH) Measured in 10 wt% CCl24 solution.

Effects of the Invention The carboxylic acid salt having a perfluorocarbon chain according to the present invention is a novel fluorine-containing compound that is not only useful as a surfactant but also as a raw material for water and oil repellents.

Claims (1)

[Claims] 1. A fluorine-containing carbon dioxide represented by the general formula (I): RfO(CH_2)nCOOH(I) (wherein, Rf represents a perfluoroalkenyl group, and n represents a number of 3 or more) Acids or their salts. 2. The fluorine-containing carboxylic acid or salt thereof according to item 1, wherein the perfluoroalkenyl group is a dimer or trimer residue of hexafluoropropene. 3. General formula (II): RfO(CH_2)nCH_2OH(II) (wherein, Rf represents a perfluoroalkenyl group, and n represents a number of 3 or more) is oxidized in an organic solvent. General formula (I): RfO(
A method for producing a fluorine-containing carboxylic acid or a salt thereof represented by CH_2)nCOOH(I) (wherein Rf and n have the same meanings as above). 4. The method according to item 3, wherein the perfluoroalkenyl group is a dimer or trimer residue of hexafluoropropene. 5. The method according to paragraph 3, wherein the organic solvent is selected from acetone, t-butyl alcohol, pyridine, chloroform and isooctane. 6. The method according to item 3, wherein the oxidizing agent is chromic acid or potassium permanganate. 9. The method according to item 3, wherein the reaction is carried out at a temperature below room temperature.