DE2120868A1 - Fluorinated sulfoxylated ampholytes and processes for their preparation - Google Patents

Description

PATENT ADVOCATE DR. HANS-GUNTHER EGGERT, DIPLOMA CHEMIST

5 KOLN-UNDEKTHAL PETER-KINTGEN-STRASSE 2 9

Cologne, April 23, 1971 Eg / Ax / Hz

Uglne Kuhlmann, Io rue du General Foy, Paris 8e / France

Fluorinated sulfoxylated ampholytes and methods am

their manufacture

The invention relates to a new class of particularly active fluorinated sulfoxylated ampholytes of the general formula

in the CL. is a straight or branched perfluorinated chain in which η is an integer between 1 and 20, a for an integer between 2 and 10, R ,. for a hydrogen atom, an alkyl radical with 1 to 6 carbon atoms or the radical ° _n ^F 2n + 1 "" ^ ^{C! H} 2 ^ a ~ ^ß0 2> ^R 2 ^ * ^{1 R} 3 ^for ^ ¹³ ^ ¹ "radicals with 1 to 3 carbon atoms, at least one of these radicals must be a methyl radical, and ρ and q stand for integers between 0 and 10.

The invention further comprises the preparation of the fluorinated ampholytes of the general formula (I) by a process in which one perfluoroamine compounds of the general formula

their production is the subject of the German patent (patent application P 21 18 241.2) of the applicant

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is, with a saturated aliphatic lactone of the formula

(III)

(CH ₂ ) _q - OO

or an α, β-ethylenically unsaturated carboxylic acid der formula

H (OH ₂ ) ₂ -CH «0H-00OH (IV)

implements.

Of the new products according to the invention, those of the above general formula are those in which R has a value of 6, 8 or 10, a has a value of 2 or 4, ρ has a value of 2 or 3 »<1 a value of 2, 3 or 4 and R ₂ and Β.-, both represent methyl radicals, are particularly interesting

According to a first method, the fluorinated Ampholytes of the general formula (I) by reacting a saturated aliphatic lactone (III) with the perfluoroamines of formula (II) · The reaction is advantageously carried out in a strongly polar solvent such as Acetone carried out. One calls the rest

) p ~ of ^{the derivative}

the procedure can be carried out by the following overall reaction scheme being represented;

R + JO.

² + ι— (0H _o ) "-00 ---» ►AN ^ ² - (0H ₀ ) -000 "(1)

A reaction of the same kind is already described in the USA patent 2,548,428 who described the manufacture of quaternary amines from tertiary amines and ß-lactone relates, the amines used being aliphatic and having various functional groups in their substituents th may contain. In the aliphatic series they have in ß-position or in a higher position to the embroidery

109847/1964

With the exception of the steric interactions in the chains with 3 or 6 carbon atoms, the functional groups of the amino group have practically no effect on the reactivity of the latter.

Under these conditions, the possibility of quaternarizing compounds containing perfluorinated chains with ß-propiolactone is surprising and remarkable

A second process for the preparation of the fluorinated ampholytes of the general formula (I) is that a molecule of an α, ß-äthyleniech unsaturated carboxylic acid (IV) is bound to the polyfluoroamines (II). this probably happens according to a mechanism that is derived from the Michael reaction · The nucleophile Group would be a nitrogen atom of the tertiary amino group. Under these conditions the overall reaction for the preparation of the fluorinated ampholyte derivatives (I) are written as follows

+ H (OH ₂ ) ^ ₂ -CH-OH-OOOH

(2)

> J

The reaction is advantageously carried out in a solvent and can be catalyzed with traces of basic reagents. As the absence of the ^{absorption band characteristic of KH 4} * at 2500 cm in the infrared spectrum shows that practically no amine salt is formed

The only limitation of this reaction is the nature of the alkylreets R ₂ and R ,, which must not be too bulky,

109847/1964

there is no steric effect around the formation of the quaternary ammonium group Oppose hindrance. These radicals must not contain more than 3 carbon atoms, and at least one of they must be a methyl radical.

Comparative measurements of the foaming capacity can be used to determine that it is not necessary for the use of the surface-active ampholytes (I) to use them very largely to clean. The presence of a small proportion of polyfluoroamines (II) in addition to the fluorinated ampholet compounds (I) even has a synergistic effect.

The new fluorinated sulfoxylated Ampholötverbindungen according to the invention find due to their surface properties, in particular due to their foaming capacity, their film-forming capacity and the strong reduction the surface tension that they cause in water and numerous solvents have many applications as surfactants in the textile industry and in the paint and coating industry.

Example 1 _GH Dissolve 50 g of CgF ^ 7-C ₂ H ₄ -SO ₄ -N- (CH ₂ ) ^^ 'in 75 ml

H 3

Acetone and then 6 g of ß-propiolactone corresponding to an excess of Jfo . The reactants are left in contact for 1 hour at room temperature and the solvent is then evaporated off. The crude product obtained is washed twice with 100 ml of ether each time to remove the excess lactone and then dried under reduced pressure. In this way 49.1 g of a white product with a melting point of 120 ° to 125 ° C. and having the following formula are obtained:

+ .CHp

CgF ₁ H ₇ -C ₂ H ₄ -SO ₂ -N- (CH ₂ ) ₂ - ⁿ CT -CH ₂ -CH ₂ -COO "

H OH,

The yield based on the fluoramine used

10 9847/1 96A

Response is 88%. A solution of 250 ppm of this compound in water lowers the surface tension of water by 72 dynes / cm to 16.3 dyn / cm at 19 »3 ° C _O

Example 2

10 g of C ₆ F ₁₅ -C ₂ H ₄ -SO ₂ NH-CCH ₂ ) ₂ -N-CCH ;,) _{2 are dissolved} in 50 ml of chloroform and 1.46 g of β-propiolactone are added. The mixture is left to react for 48 hours at room temperature and the solvent is then evaporated off. After washing with 20 ml of chloroform, filtration and drying under reduced pressure, 10.9 g of a white product are obtained which ^{melts at 102 °} C. and has the following formula:

C ^ -F, -, - CpH ^, - SOp-NH-CCHp ^ pNQCH ^^ pCHp ~ "CHp" "COO

The yield of the reaction, based on the fluoramine used, is $ 95. A solution of 250 ppm of this ampholyte lowers the surface tension of the water to 16.8 dynes / cm at 17 ° C

Example 5

9.5 g of C _1Q F ₂₁ -C ₂ H ₄ -SO ₂ -NH-CCH ₂ ) ₂ -N-CCH,) _{2 are dissolved} in 70 ml of ethyl acetate and 1.00 g of β-propiolactone is added. After 48 hours, the solvent is evaporated off and a white solid is obtained, which is washed with 20 ml of ethyl acetate. After drying under reduced pressure, 9 »35 g of a white product which melts at 125 ° C. and has the following formula are obtained:

-C ₂ H ₄ -SO ₂ NHC CH ₂ ) ₂ NC CH ₃ ) ₂ CH ₂ -CH ₂ -C00 "

The yield of the reaction is 90%. A solution of 250 ppm of this compound lowers the surface tension of the water to 32 dynes / cm at 18 ^° C.

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Claims (2)

Claims / ίο) Fluorinated sulfoxylated ampholytes of general formula in the ^ 2n + 1 ^e i ⁿ e straight or branched perfluorinated chain in which η is an integer between 1 and 20, a for an integer between 2 and 10, R ₁ for a hydrogen atom, an alkyl radical with 1 to 6 C Atoms or the radical ^G _n ^{: P} 2n + 1 "^ ^GH 2 ^ a" ^S0 2 'R2 and R, represent alkyl radicals with 1 to 3 carbon atoms, at least one of these radicals must be a methyl radical and ρ and q. are integers between 0 and 10. 2. procedural r s for preparing fluorinated sulfoxylated ampholyte according to claim 1, characterized in that Polyfluoramine of formula at room temperature with a saturated aliphatic lactone of the formula q. - 9 ° (III) implements. ο Process for the production of fluorinated sulfoxylated ampholytes according to Claim 1, characterized in that polyfluoramines of the formula (II) are mixed with an oc, ß-ethylene carboxylic acid H (CH ₂ ) ₂ -CH »CH-COOH (IV) converts at ambient temperature.
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