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Publication numberUS3864396 A
Publication typeGrant
Publication dateFeb 4, 1975
Filing dateDec 8, 1972
Priority dateDec 10, 1971
Also published asDE2161341A1
Publication numberUS 3864396 A, US 3864396A, US-A-3864396, US3864396 A, US3864396A
InventorsGerlach Klaus, Staffe Adolf
Original AssigneeBayer Ag
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Acylated perfluoroalkanesulphonamides
US 3864396 A
Abstract
Perfluoroalkanesulphonamides of the formula IN WHICH A, R1, R2, R3, Rf, m, n, x and y have the meaning given in the disclosure, and a process for their manufacture. The perfluoroalkanesulfonamides are excellent oleophobic agents.
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Description  (OCR text may contain errors)

United States Patent [191 Staffe et al.

[ 1 Feb. 4, 1975 ACYLATED PERFLUOROALKANESULPHONAMIDES [75] Inventors: Adolf Staffe, Oplanden; Klaus Gerlach, Cologne, both of Germany [73] Assignee: Bayer Aktiengesellschaft,

Leverkusen, Germany 22 Filed: Dec. 8, 1972 21 Appl,N0.:3l3,276

[30] Foreign Application Priority Data Dec. 10, 1971 Germany 216134] [52] U.S. Cl. 260/556 F, 252/875, 260/465.5 R, 260/543 R, 260/543 F, 260/553 R, 260/553 A, 260/556 A, 260/583 P [51] Int. Cl. C07C 143/74 [58] Field of Search 260/556 F, 465.5 R, 553 R, 260/553 A [56] References Cited UNITED STATES PATENTS 8/1956 Brown et al. 260/556 F 8/1957 Ahlbrecht et al. 260/556 F Primary Examiner-HenryR. Jiles Assistant Examiner-S. D. Winters Attorney, Agent, or Firm-Plumley & Tyner [57] ABSTRACT Perfluoroalkanesulphonamides of the formula their manufacture. The perfluoroalkanesulfonamides are excellent oleophobic agents.

7 Claims, No Drawings ACYLATED PERI-LUOROALKANESULPHONAMIDES The invention relates to perfluoroalkanesulphonamides; more particularly it concerns perfluoroalkanesulphonamides of the formula with the proviso that R and R only represents an optionally substituted alkyl group if the nitrogen atom to which the two radicals are bonded is an amine nitrogen atom or a sulphonamide nitrogen atom; the invention further relates to a process for the manufacture of the perfluoroalkanesulphonamides of the formula (I) and to their use as oleophobic agents.

Possible alkylene groups A are above all alkylene radicals with 2 to ID, preferably with 2 or 3, C atoms, for example the ethylene, ethylidene, propylene-(1,3), butylene-( 1,4), hexylene-( 1,6) and 4-oxaheptylene- (1,7) group. 7

Examples which may be mentioned of optionally substituted alkyl groups which R and R can be are: lower alkyl radicals, for example C,C,-alkyl radicals, such as the methyl, ethyl, n-propyl, n-butyl and sec.-butyl radical, and lower alkyl radicals substituted by nitrile or lower alkoxy groups, such as the Z-methoxyethyl, 3- methoxypropyl, Z-ethoxyethyl, 3-ethoxypropyl and 2- cyanoethyl radical. 7

Examples of carboxylic acids from which R, is derived as an acyl radical are both aromatic and saturated or unsaturated aliphatic monocarboxylic or dicarboxylic acids. As aromatic carboxylic acids, benzoic acid.

may especially be mentioned, and as saturated or unsaturated aliphatic carboxylic acids lower monocarboxylic acids may above all be mentioned, such as acetic acid, propionic acid, butyric acid, acrylic acid and methacrylic acid and also lower dicarboxylic acids, such as succinic acid, adipic acid and maleic acid.

As optionally substituted carbonamide groups which R can be there may be mentioned carbonamide groups substituted by C -C -alkyl, cyclohexyl or aryl groups, such as the methyl-, methoxymethyl-, ethyl-, cyclohexyl, phenyland tolyl-carbonamide group.

As examples of representatives of the perfluoroalkanesulphonamides of the formula (I), according to the invention, there may be mentioned:

c F so -mr-ca' The perfluoroalkanesulphonamides of the formula (I), according to the invention, are obtainable in various ways; preferably, they are obtained by reacting polyamines of the formula in which A and n have the meaning indicated under the formula (l) with perfluoroalkanesulphonyl halides of the formula (Ill) in which R, and m have the meaning indicated under the formula (l) and in which X represents chlorine or preferably fluorine, and optionally acylating the resulting polyperfluoroalkane-sulphonyl-polyamines in a manner which is in itself known and/or alkylating them in a manner which is in itself known.

Another possible method of manufacture consits of first acylating the polyamines of the formula (H) in a manner which is in itself known and to react the acylated polyamines of the formula l flf tAtw -t t l (41 (Iv) in which n and y have the meaning indicated under the formula (l) with perfluoroalkanesulphonyl halides of the formula (III), in the manner described for the polyamines.

The reaction of the polyamines (II) with the perfluoroalkanesulphonyl halides (lll) is carried out at temperatures of to 150C, preferably 40 to 90C, in the presence of acid-binding agents, such as inorganic bases, for example potassium carbonate, or organic bases, for example tertiary amines, such as triethylam- To introduce the acyl and carbonamide groups the poly-perfluoroalkanesulphonyl-polyamines are reacted in a manner which is in itself known,at temperatures of 0 to l00C, preferably at 30 to 60C, optionally in solvents which are inert under the reaction conditions, such as pyridine. benzene, toluene or chlorobenzene, with compounds which react with basic nitrogen atoms to form amides, such as acyl halides, for example benzoyl chloride, acetyl chloride, propionyl chloride, butyryl chloride, acrylic acid chloride, methacrylic acid chloride, choroformic acid methyl ester or chloroformic acid ethyl ester; acid anhydrides, for example acetic anhydride, succinic anhydride and maleic anhyd'ride; carboxylic acid esters, for example acetic acid methyl ester, propionic acid methyl ester and benzoic acid methyl ester; isocyanates, for example methylisocyanate, methoxymethylisocyanate, ethylisocyanate, cyclohexylisocyanate, phenylisocyanate and tolyisocyanate; and inorganic cyanates, for example potassium cyanate.

To introduce the alkyl groups, the optionally acyl' ated poly-perfluoroalkanesulphonyl-polyamines are converted, in a manner which is in itself known, into the alkali compounds of the sulphonamides, for example by reaction of the sulphonamides with sodium methylate in absolute methanol, and the alkali compounds are reacted, optionally in a solvent which is inert under the reaction conditions, with alkyl halides of the fomula RX, and/or RX Instead of starting from polyamines of the formula (ll) it is also possible, in manufacturing the compounds of the formula (I) according to the invention, to start from diamines containing cyanoalkyl groups, for example N-cyanoethylethylenediamine, to react these with perfluoroalkanesulphonyl halides in the manner described above for the polyamines (ll), and to reduce the resulting bis-perfluoroalkanesulphonylcyanoalkylamines to the corresponding bisperfluoroalkanesulphonyLaminoalkyl-amines. The amines thus obtainable can optionally subsequently be further aeylated and/or alkylated as described.

The compounds according to the invention, of the formula (I) are valuable agents for the oleophobic finishing of materials made of paper, wood, textiles and yarns.

It should be emphasised that an excellent oleophobie effect is achieved with the perfluorobutyl group containing sulphonamides of formula (I). This is surprising since hitherto the opinion was held amongst experts (see Textilvercdlung 2/ 1967 page 463) that for oleophobic agents based on perfluoroalkanesulphonamides the chain length of the perfluoroalkyl radical had to be 6 to 8 C atoms.

EXAMPLE l 604 g (2 mols) of perfluoro-n-butanesulphonic acid fluoride are added dropwise, at a temperature of 89C, to a mixture of 103 g (1 mol) of diethylenetriamine, 505 g (5 mols) of triethylamine and 67.5 g (0.5 mol) of N-dimethylbenzylamine at such speed that the temperature of the reaction mixture does not drop below C. To complete the reaction, the reaction mixture is stirred for 5 hours at 80C. After distilling off the triethylamine, the residue is dissolved in 550 ml of pyridine. 104 g (l mol) of methacrylic acid chloride are slowly added dropwise to this solution at 35 to 45C. The reaction mixture is stirred for a further 6 hours. The bulk of the pyridine is then distilled off under reduced pressure and the residue in the flask is poured into 1.000 ml of water. The reaction product which has precipitated is filtered off and washed with water until it reacts neutral.

The N,N-Bis-( 2-perfluorobutanesulphonylaminoethylJ-methaerylic acid amide I CH -C 3 n (molecular weight 735) precipitates in the form of a yellowish brown amorphous powder in a yield of 647 I5 g 88% of theory).

perfluorobutanesulphonylaminoethyl)-methacrylic acid amide described in Example 1, in acetone, squeezed out to a weight increase of 50% and dried for l minutes at 100C. This fabric (deposit of oleophobic agent: 0.5 per cent by weight) receives a rating of 100 to H0 in the 3M test.

The oleophobic effect of the fabric, paper and wood products described was assessed in accordance with the socalled 3M oil repellency test" (Crajeck. Petersen,

t0 Textile Research Journal 32. page 320 to 331 (1960) with heptane-parafl'in oil mixtures. in the assessment. I50 denotes the best achievable rating and 50 the worst rating. The individual samples were assessed immediately after drying.

We claim:

1. Perfluoroalkanesulphonamide of the formula EXAMPLE 2 604 g (2 mols) of perfluoro-n-butanesulphonic acid fluoride are slowly added dropwise at a temperature of 89C to a mixture of 146 g (1 mol) of triethylenetetramine and 606 g (6 mols) oftriethylamine. To complete the reaction, the reaction mixture is stirred for a further 5 hours at 85C. After distilling off the triethylamine. the residue is dissolved in 600 ml of pyridine. 208 g (2 mols) of methacrylic acid chloride are slowly added dropwise to the solution at to C. The reaction mixture is stirred for a further 6 hours at room 37 temperature. The bulk of the pyridine is then distilled off under reduced pressure and the residue in the flask is poured into L000 ml of water. The reaction product which precipitates is filtered off and washed with water until it reacts neutral.

The N,N-bis-( 2-perfluorobutanesulphonylaminoethyl)-N,N'-bis-methacryloyl-ethylenediamine on -c on -c 5" 5" CH CH CH -NHSO C F (molecular weight 846) is obtained in the form of a brownish amorphous powder in a yield of 778 g 92% of theory).

EXAMPLE 3 Cotton fabric was impregnated with a 1% strength solution of the N,N-bis-(2- in which R is carbonyl, oxalyl, succinyl, adipyl, or maleoyl;

R and R independently of one another are hydrogen; C -C alkyl; or C,C, alkyl substituted by nitrile or lower alkoxy;

A is Crcw-alkylene or C -C alkylene interrupted by oxygen;

R is perf'luorinated butyl; and m is 1 or 0.

3. lerfluoroalkanesulfonamide of claim 2 having the formula

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2759019 *Aug 9, 1954Aug 14, 1956Minnesota Mining & MfgPerfluoro amine compounds and quaternary derivatives
US2803656 *Jan 23, 1956Aug 20, 1957Minnesota Mining & MfgFluorocarbonsulfonamidoalkanols and sulfates thereof
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3917691 *Nov 12, 1973Nov 4, 1975Nat Starch Chem CorpPerfluoro alkyl sulfonamides useful as water and oil repellency agents
US4149979 *Jun 26, 1978Apr 17, 1979Cassella AktiengesellschaftConditioning and water-repellent agents for cellulose-containing textiles and leather
US4163754 *Jan 18, 1978Aug 7, 1979Ici Americas Inc.Fluorinated sulfonamides
US4175096 *Aug 30, 1977Nov 20, 1979Bayer AktiengesellschaftAlkoxylated perfluoroalkanesulphonamides
US7547732 *Aug 30, 2005Jun 16, 20093M Innovative Properties CompanyCompositions of fluorochemical surfactants
US20070049646 *Aug 30, 2005Mar 1, 2007Moore George G ICompositions of fluorochemical surfactants
Classifications
U.S. Classification564/48, 564/57, 558/430, 252/8.62, 558/437, 564/59, 564/82, 558/393
International ClassificationD06M13/405, D21H17/11, C07C67/00, D21H17/00, D21H17/09, C07C301/00, D21H17/07, D06M13/322, C07C303/40, B27K3/34, C07C311/00, D06M13/418, D06M13/02, D06M13/402, C07C311/01, C07C311/05, C07C303/00, D06M13/41, D06M13/00, C09K3/00, C07C303/38, D06M13/438
Cooperative ClassificationD21H17/09, D06M13/418, C07C311/05, D06M13/405, D06M13/41, D21H17/11, D06M13/438
European ClassificationD06M13/41, D06M13/418, C07C311/05, D21H17/11, D06M13/438, D06M13/405, D21H17/09