JPH07145119A - Fluorine-containing amine - Google Patents

Abstract

PURPOSE:To obtain the subject new compounds useful as an intermediate for a fluorine- containing cationic surfactant, etc., having uses as a surface modifier, etc., for fiber, a metal and a resin, etc. CONSTITUTION:This fluorine-containing amine is expressed by formula I [Y is COO, CONH or CON(CH3); R1 and R2 are H, a 1-5C a1kyl, benzyl; (n) is 6-12; (m) is 2-6], e.g. a compound expressed by formula II and further this fluorine-containing quaternary ammonium salt is expressed by formula III [R3 is H, a 1-5C alkyl or benzyl; (k) is 1-6; Z is a mono- to a hexavalent anion], e.g. a compound expressed by formula IV. The fluorine-containing amine expressed by formula I is obtained by reacting a compound expressed by formula V (X is a halogen; R is an alkyl) with a perfluoroalkene expressed by the formula CnF2n, providing a compound expressed by formula VI, then hydrolyzing the prepared compound, subsequently neutralizing the hydrolyzed compound, providing a compound expressed by formula VII, then treating the resultant compound with a halogenating agent. affording a compound expressed by formula VIII and finally reacting the prepared compound expressed by formula VIII with a compound expressed by formula IX. Furthermore, the compound expressed by formula III is obtained by treating the compound expressed by formula I with a quaternizing reagent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel fluorine-containing amine useful as an intermediate for fluorine-containing cationic surfactants and the like, which is used as a surface modifier for fibers, metals and resins.

[0002]

2. Description of the Related Art Fluorine-containing amines conventionally known as raw materials for producing fluorine-containing dyes and polymers (for example, fluorine-containing polyamide, fluorine-containing polyimide, etc.) are rigid anilines in which an amino group is directly bonded to a benzene ring. Since it is a derivative, it is problematic as a raw material for surface modifiers such as fibers and resins (see, for example, Japanese Patent Publication No. 62-178551,
(See Japanese Patent Publication Nos. 2-117648 and 4-26658). Further, although a fluorinated amine useful as a raw material for producing a fluorinated cation surfactant and the like is known,
(See Japanese Patent Publication No. 58-38475), in the case of the fluorine-containing amine, the saturated fluorine-containing group is bonded to the benzene ring through an ether bond, and part of the molecule is rigid. When a fluorinated cation surfactant obtained from a fluorinated amine is used as a surface modifier for fibers, resins, etc., the adsorption power for fibers, resins, etc. is weak, and it is difficult to obtain a sufficient surface modification effect. is there.

[0003]

DISCLOSURE OF THE INVENTION The present invention solves the above problems of conventional fluorine-containing amines and has applications as excellent surface modifiers for various fibers, resins and metals. The purpose of the present invention is to provide a fluorine-containing amine useful as an intermediate such as an ionic surfactant.

[0004]

That is, the present invention has the general formula
(I):

[Chemical 3] [In the formula, Y is -COO-, -CONH-, or -CON
(CH ₃₎ - indicates, R ₁ and R ₂ are hydrogen atoms, independently of one another, an alkyl group or a benzyl group having 1 to 5 carbon atoms, n represents a number of 6 to 12, m is 2 To a number of 6] and a quaternary ammonium salt thereof.

Examples of the perfluoroalkyl group in the general formula (I) include a group derived from a dimer or trimer of hexafluoropropene or a trimer to pentamer of tetrafluoroethylene. From the viewpoint of ease of use, a group derived from a dimer or trimer of hexafluoropropene is preferable. In the general formula (I),
Y is -COO -, - CONH- or -CON (CH ₃₎
Represents a divalent residue represented by-, R ₁ and R ₂ independently of each other represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a benzyl group, and n represents a number of 6 to 12 , M is 2
Indicates a number of ~ 6.

The method for producing the fluorine-containing amine represented by the general formula (I) is not particularly limited, but a suitable production method is illustrated below. First, the following formula (II): XCH ₂ COOR (II) (wherein, X represents a halogen atom, and R represents 1 to 1 carbon atoms).
A halogenated acetic acid ester represented by the following formula (III): C _n F _2n (III) (in the presence of an alkali metal fluoride and iodide in an aprotic polar solvent). In the formula, n has the same meaning as described above, and is reacted with a perfluoroalkene represented by the general formula (I
_{V): C n F 2n +} 1 -CH 2 -COOR (IV) ( wherein, R and n are preparing fluorinated esters represented by the same as is). As the aprotic polar solvent, a ketone solvent (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), an ether solvent
(For example, tetrahydrofuran, diethyl ether, dimethyl ether, dioxane, etc.) and an amide solvent (for example, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylimidazolidinone,
(N-methylpyrrolidone, etc.) and the like, but an amide-based solvent having an excellent dissolving power is particularly preferable.

KFNa as an alkali metal fluoride
F, RbF and CsF are exemplified, but KF is particularly preferable from the viewpoint of handling and reactivity, and KI, NaI, RbI and C are used as the alkali metal iodide.
sI is exemplified, but from the viewpoint of handling and reactivity, K
I is particularly preferred.

In the above reaction, the use ratio of halogenated acetic acid ester, perfluoroalkene, alkali metal fluoride and alkali metal iodide is not particularly limited, but usually perfluoro halogenated acetic acid ester per mole is used. Alkane 1-2 moles, alkali metal fluoride 1-2 moles and alkali metal iodide 0.
It is from 01 to 0.1 mol. In addition, the above reaction is usually performed under normal pressure at room temperature to 60 ° C.

Next, the fluorine-containing ester represented by the general formula (IV) is hydrolyzed using an alkaline aqueous solution, for example, an aqueous solution of sodium hydroxide, potassium hydroxide or the like, and the hydrolyzate is treated with an acid such as hydrochloric acid or sulfuric acid. By neutralizing with.
Following formula (V): (in wherein, n are the same as defined _{above) C n F 2n + 1 -CH} 2 -COOH (V) to prepare a fluorine-containing carboxylic acid represented by.

Next, by treating the fluorine-containing carboxylic acid with a halogenating agent such as thionyl chloride,
Following formula _{(VI): C n F 2n} + 1 -CH 2 -COX (VI) ( wherein, X and n are the same as defined) to prepare a fluorine-containing acid halide represented by. In this case, a catalyst such as N, N-dimethylformamide is preferably used, and the treatment temperature is preferably 50 ° C. to the boiling point of the halogenating agent.

Finally, the fluorine-containing acid halide is represented by the general formula (VII):

[Chemical 4] (Wherein Z represents —OH, —NH ₂ or —NH (CH ₃ ), and R ₁ , R ₂ and m have the same meanings as described above) to give a compound represented by the above general formula. formula
A fluorinated amine represented by (I) is obtained.

Examples of the compound represented by the general formula (VII) include the following: HO (CH ₂ ) ₂ N (CH ₃ ) ₂ HO (CH ₂ ) ₃ N (CH ₃ ) ₂ HO (CH ₂ ) ₆ N (CH ₃ ) ₂ H ₂ N (CH ₂ ) ₂ N (CH ₃ ) ₂ H ₂ N (CH ₂ ) ₃ N (CH ₃ ) ₂ H ₂ N (CH ₂ ) ₆ N (CH ₃ ) _{2 HN (CH 3) (CH 2} ) 2 N (CH 3) 2 HN (CH 3) (CH 2) 3 N (CH 3) 2 HN (CH 3) (CH 2) 6 N (CH 3) 2

[Chemical 5]

[Chemical 6]

[Chemical 7] _{HO (CH 2) 3 N (} C 4 H 9) 2 HO (CH 2) 2 N (C 4 H 9) 2

[Chemical 8]

In this reaction, a tertiary amine (eg, triethylamine, trimethylamine, N, N-dimethylaniline, etc.) may be used as a deoxidizing agent, and the above ether-based solvent, nitrile-based solvent and In addition to an aprotic polar solvent such as an amide solvent, a solvent such as a halogen solvent or an aromatic solvent may be used. The reaction ratio is preferably 2 to 2.5 mol of the compound represented by the general formula (VII) per mol of the halide represented by the general formula (VI), and the reaction temperature is 0 to 100 ° C., particularly 10 to 10.
40 ° C. is preferred.

The present invention provides the following formula (VII) obtained by treating the fluorine-containing amine represented by the general formula (I) obtained by the above-mentioned production method with a quaternizing reagent.
I):

[Chemical 9] (In the formula, Y, R ₁ , R ₂ , n and m have the same meanings as described above, R ₃ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a benzyl group, and k represents 1 to 6). Indicates the number, Z is 1
To a hexavalent anion) are also included.

In the general formula (VIII), R ₃ is a hydrogen atom,
It represents an alkyl group having 1 to 5 carbon atoms or a benzyl group, k represents a number of 1 to 6, and Z represents a monovalent to hexavalent anion capable of forming a quaternary ammonium salt. 1-6
Examples of the valent anion include, but are not limited to, the following ions: Halogen ion (F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ ) CH ₃ (CH ₂ ) _{0 to 6} COO ^{− −} OOC ^{_{(CH 2) 0~6 COO - [}} CH 2 N (CH 2 COO -) 2] 2 [BF 4] - [PF 6] - [PW 12 O 40] 3- [V 10 O 28] 6- [SiO ^{_{7] 6- [PO 4] 3-}} [SO 4] 2- CF 3 SO 3 -

[Chemical 10]

[Chemical 11]

[Chemical 12]

[Chemical 13]

[Chemical 14]

[Chemical 15]

[Chemical 16]

Fluorine-containing fourth group represented by the general formula (VIII)
Among the quaternary ammonium salts, a quaternary ammonium salt in which Z is a halogen ion is a fluorine-containing amine represented by the general formula (I) represented by the general formula (IX): R ₃ · X (IX) (wherein R ₃ And X have the same meanings as above).
As the reaction solvent, an alcohol solvent may be used in addition to the above-mentioned ketone solvent or ether solvent. The reaction temperature depends on the reactivity of the halide represented by the general formula (IX), but is usually 0 to 100 ° C. In general, iodide is highly reactive, so it is preferable to carry out the reaction at 0 ° C. to room temperature, and for other halides, it is carried out under heating or heating.

The quaternary ammonium salt obtained by the above reaction, that is, the following formula (X):

[Chemical 17] (Wherein Y, R ₁ , R ₂ , R ₃ , n, m and X have the same meanings as described above), the quaternary ammonium salt is represented by the following formula (XI): Z ′ · kM (XI (Wherein k is as defined above, Z'represents an anion of 1 to 6 valences excluding halogen ions, and M represents an alkali metal ion). A fluorinated quaternary ammonium salt represented by the general formula (VIII) other than the quaternary ammonium salt can be prepared. This reaction may be carried out according to the usual conditions for salt exchange reaction. For example, the general formula (X)
When the quaternary ammonium salt represented by the formula (4) is sparingly soluble or insoluble in water, the quaternary ammonium salt is dissolved in alcohol-containing water, and this is mixed with an aqueous solution of an alkali metal salt represented by the general formula (XI). The reaction may be performed at room temperature or under heating.

[0018]

EXAMPLES The present invention will be described below with reference to examples. Example 1 A perfluoro-2-methyl-2-pentene 36 was placed in a reaction vessel equipped with a cooling tube, a thermometer, a stirrer and a dropping funnel.
0 g (1.2 mol), ethyl bromoacetate 167 g (1.0
Mol) N, N-dimethylacetamide (1 liter) and then thoroughly dried KF (116 g, 2.0 mol)
And KI 33.2 g (0.2 mol) were added, and the mixture was stirred under stirring to give 6
The reaction was carried out at 0 ° C for 15 hours. The reaction mixture was washed with an aqueous solution of sodium sulfite and water, and then subjected to dehydration, concentration, and distillation treatments to give compound (1) (b.
350g (yield 89.4).
%). The physical properties of compound (1) are shown in Table 1.

[Chemical 18]

210 g of the compound (1) was added to 600 ml of 10% potassium hydroxide in ethanol, reacted at 80 ° C. for 2 hours, neutralized with 70% of 10% hydrochloric acid, and washed with water, dehydrated and dried. By the compound
174 g of (2) was obtained. Further, the compound (2) 174 was placed in a reaction vessel equipped with a cooling tube, a thermometer, a stirrer, and a dropping funnel.
Add a few drops of g, N, N-dimethylformamide, and heat at 50 ° C.
After heating to 163 g, 163 g of thionyl chloride was added dropwise. Then, the temperature was raised to the boiling point of thionyl chloride and the reaction was carried out for 5 hours. After the completion of the reaction, the reaction mixture was treated with n-hexane and filtered to remove the n-hexane to obtain the compound (3). Table 1 shows the physical properties of the compounds (2) and (3).

[Chemical 19]

[Chemical 20]

24.5 g (0.24 mol) of N, N-dimethyl-1,3-propanediamine and 24.8 g (0.245 g) of triethylamine were placed in a reaction vessel equipped with a condenser, a thermometer, a stirrer and a dropping funnel. Mol), diethyl ether 500m
l, and while stirring in an ice bath while cooling, the compound
(3) 85.2 g (0.215 mol) of diethyl ether 10
A solution dissolved in 0 ml was added dropwise. After completion of dropping, the mixture was refluxed for 3 hours. After completion of the reaction, the reaction solution was transferred to a separating funnel, washed with 100 ml of 10% NaOH aqueous solution once, then with 100 ml of water twice, and further washed with 100 ml of saturated saline solution four times. The diethyl ether solution was dried over anhydrous sodium sulfate, and then diethyl ether was removed under reduced pressure to obtain 93.6 g of a crude reaction product. To this was added 500 ml of acetonitrile, the precipitated by-product was filtered off, the filtrate was placed in a reaction vessel, and 50.4 g (0.35 mol) of methyl iodide was further added dropwise at room temperature with stirring. After reacting for 2 hours, the precipitated solid was filtered off and the solid was recrystallized from acetonitrile to obtain 59.9 g of compound (4). The physical properties of compound (4) are shown in Table 1.

[Chemical 21]

[0021]

[Table 1]

Example 2 101 g (0.17 mol) of compound (4) and 300 ml of water were placed in a reaction vessel equipped with a condenser, a thermometer, a stirrer and a dropping funnel, and the mixture was stirred while heating at 50-60 ° C. Under this, add 36.8 g (0.34 mol) of sodium borofluoride to 100 m of water.
The solution dissolved in 1 was added dropwise. After completion of dropping, the mixture was stirred for 3 hours. After completion of the reaction, the precipitated solid was filtered off, and this solid was recrystallized from a mixed solvent of hexane to give compound (5)
64.4 g was obtained (yield 67.2%). Table 2 shows the physical properties of the compound (5).

[0023]

[Chemical formula 22]

[0024]

[Table 2]

[0025]

INDUSTRIAL APPLICABILITY The fluorine-containing amine according to the present invention has low rigidity as compared with conventional fluorine-containing amines, and has a fluorine-containing group having excellent properties such as water / oil repellency and antifouling property in the molecule. Since it has an amino group that has strong adsorptivity to various fibers, resins and metals, it is used as a surface modifier, emulsifier, dispersant, penetrant, etc. for fibers, resins and metals. It is a novel compound that is particularly useful as an intermediate for ionic surfactants and the like. The fluorine-containing amine according to the present invention is also useful as a raw material for a fluorine-based phase transfer catalyst.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hiroyuki Obama 1-1 Oike-cho, Kosai-cho, Koga-gun, Shiga Prefecture Within Neos (72) Inventor Masafumi Takeshita 6-2-1 Kano-cho, Chuo-ku, Kobe-shi, Hyogo Issue Neos Co., Ltd. (72) Inventor Nobuyuki Nakayama 1-1 Oikemachi, Kosai-cho, Koga-gun, Shiga Stock Company Neos

Claims (2)

[Claims] 1. General formula (I): [In the formula, Y is -COO-, -CONH-, or -CON
(CH ₃₎ - indicates, R ₁ and R ₂ are hydrogen atoms, independently of one another, an alkyl group or a benzyl group having 1 to 5 carbon atoms, n represents a number of 6 to 12, m is 2 A fluorine-containing amine represented by the formula 2. General formula (VIII): (In the formula, Y, R ₁ , R ₂ , n and m have the same meanings as described above, R ₃ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a benzyl group, and k represents 1 to 6). Indicates the number, Z is 1
To a hexavalent anion).