DE1938544A1 - Fluorinated quaternary ammonium salts and processes for their preparation - Google Patents

Description

DR. ILSE RUCH PATENT ADVOCATE MUNICH iQonr / /

REICHENBACHSTR. 51 I CJ 0 0 ü 4 4

TEL 863251

Polio A / 13967

R / P / tf

Alled Chemical Corporation, New York, N.Y., USA

Fluorinated QuaternKre Ammonium Salts and Processes for their manufacture

Various fluorine-containing compounds are also used been made to make textiles and paper Sl- and water-repellent close. These fluorine-containing compounds generally consist of an active component Group bound · fluorinated alkyl chain. Their oleo and hydrophobicity are at least partly the low Surface energy of the fluorinated alkyl chain attributed to formed surface. The proportion of the molecule to which the fluorinated alkyl chain is attached the bond between the fluorinated alkyl chain and the surface of the support. This bond does not affect only the degree of orientation and packing of the fluorinated groups of the fluorinated alkyl chains and thus the oleo- and hydrophobicity of the agent, but also its durability the oleo- and hydrophobicity imparted to a textile or paper with repeated dry cleaning and washing.

90988 6/1668

The functional part of the molecule also partly determines the solubility of the compound. In technology such Means from a liquid medium that consists of economy = An aqueous medium is preferred for high reasons Carrier applied. Most of these remedies are, however Insoluble in water and therefore cannot be applied from an aqueous solution but must be applied from an aqueous emulsion. However, emulsions tend to coagulate when they are strong be subjected. This can lead to extraordinary difficulties if the funds are increased since the shearing action exerted by the nip rollers can cause coagulation. The coagulated agent then sticks to the rollers and is taken up by the fabric at a given time, making it streaky and becomes blotchy.

Furthermore, it is due to the functional part of the molecule at least partially the choice of an optional. For binding the agent to the carrier, in particular a carrier Cellulose base / catalyst to be used, for example an acid or a base, determines * fabric Cellulose bases are often subjected to further treatments, for example embossed or crease-proof made, what usually acidic or basic catalysts> and / or chemicals are used. Fluorine-containing Oil and water repellants that use both acidic as well as basic catalysts are compatible with all such further treatments insensitive.

The object of the invention is to find water-soluble or dispersible oil- and water-repellent agents for the treatment of textiles, paper and other fiber materials * in particular on the basis of chemically modified cellulose, which both

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ORIGINAL

with acidic as well as with basic catalysts to this Materlallen can be bound.

The invention relates to fluorinated quarternaries General form ammonium salts

0 item ¹

■ ». 'Θ

in which R _{f is} a perfluoroalkyl group with 3 to 17 carbon atoms or a group of the general formula:

CF-0- (CF ₂ ) _v - (CF ₂ CF ₂ ) _m - (CH ₂ CH ₂ ) _n - (CM ₂ ) _u

in which each of the groups R, which may be the same or different »a fluorine atom or a Is a fluoroalkyl group of up to 9 carbon atoms, or 2 of the groups R together are a fluoroalkylene group having up to 18 carbon atoms, with at least one of the groups R being a fluorine atom 1st; u and v, which can be the same or different « Are 0 or 1; m and n, which can be the same or different, are 0 or integers from 1 to 20, where m + η 0 to 20 1st, m at least 1 1st if ν equals 0 and ν 0 1st if m + η + u is greater than 0 is; M is a hydrogen or fluorine atom, namely

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a material at om let, if η is greater than 0)

χ an integer from 2 to 6, preferably 2 to 4 istι y is an integer from 1 to 4 1st)

Z is a hydrogen atom, an aoyl group of the formula -CO-R _f , in which R _{f has} the meaning given above; a vinyl sulfone group from Ponnelt

in which ρ is 0 or 1, each of the groups R, which can be the same or different, is a hydrogen atom or an alkyl or substituted or unsubstituted aryl group and V? an alkylene, arylene or aralkylene \ or a radical of an adduct of a sulfone and a tertiary amine of the formula *

-CHR ² -CHR ² -S0 ₂ - (R ⁵ SO ₂ )

in which R, R ^ and ρ have the meaning given above and -N J is a pyridyl, quinolinyl or methyl-substituted pyrldyl group)

Z is a hydrogen atom, an acyl group of the formula -C as defined above, a vinyl sulphon group as defined above, a residue of an adduct of a sulfon and a tertiary AoIn, as defined above, or a group of the formula -C _x H _2x -NH -Z, in which χ and Z have the meanings given above, where the groups Z ¹ , when y is greater than 1, can be the same or different)

X a halogen, - Sulphate, hydrogen sulphate, phosphate or hydrogen phosphatlon

q a whole number from 1 to 4 equal to the number of adduct groups

Sulfone / tertlKr is anine in the salt; and

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r is an integer from 1 to 3 equal to the valence of the Is anion;

with the proviso that the salt contains at least one acyl group of the formula CO-R _f and at least one sulfone / tertiary amine adduct group.

The alkylene group “(C _x H _2x )” ^{can be} straight-chain or branched and preferably contains 2 to 4 carbon atoms; the benzyl, 'PhenJÜhyl or xylyl group. R ² is expediently an alkyl radical having 1 to 6 carbon atoms, for example a methyl, ethyl, propyl or hexyl radical or an isomer thereof, or an aryl radical such as a phenyl or naphthyl radical or a substituted derivative thereof, for example the o-, m- or p ~ Toluy! group, the o-, m- or p-chloropheny! group or the p-nitrophenyl group.

The salts can be prepared by adding a divinyl sulfone adduct with a salt of a heterocyclic tertiary amine and a salt-forming acid.

The process of the invention for making the new fluorinated quaternary ammonium salts is thus through characterized in that one has a divinyl sulfone adduct of the general form

in which R _f , χ and y have the meanings given above, Q is a hydrogen atom, an acyl group of the formula -C0-R _f , as defined above, or a vinylsulfone group, as defined above, and Q is a hydrogen atom, an acyl group

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of the formula -CO-R _1. , a vinyl sulfone group as defined above, or a group of the formula -C _x H _2x -HNQ, ^{in which x 1} ^ ^{Q have} the meanings given above, with the proviso that the divenyl sulfone adduct contains at least one acyl group of the formula -CO-Rf and at least one vinyl sulfone group; with a salt of a heterocyclic tertiary amine, namely a halide, sulfate or phosphate of pyridine, quinoline or a methyl-substituted pyridine.

Suitable salts of heterooyolecular amines are the halides, . i.e. the fluorides, chlorides, bromides and iodides, as well as "the sulfates or phosphates of pyridine, the methyl-substituted pyridines, i.e. the ploolins, lutldines and collidines, and quinoline.

The divinyl sulfone adduct can be prepared by a corresponding fluorinated polyamide with a vinyl sulfone, which can be substituted or unsubstituted and which, when substituted, only one substituent on each Contains vinyl group and the general formula

CHR ¹ ^ R ¹ -SO ₂ - (R ^ SO ₂ ) P-CR ¹ -OHR ¹

t in which R, Fr and ρ have the meanings given above,

has implemented. Examples of suitable vinyl sulfones are Divinyl, dipropenyl, diisopropenyl, distyryl, Bis- (1-hexenyl) -, Bls- (a- & thylvinyl) -, Bis- (a-n-butylvinyl) - =. and bis (o-phenyl-vinyl) sulfonyl, 2-bis (vinyl-sulfonyl) » «Than; 1,2-BI8 ° (styrylsulfonyl) -ttthani 1,4-bis (α-ethylvinylsulfonyl) -butane and 14-bis (vinyXsulfonyl) benzene.

The fluo- red polyamide reacted with the vinyl sulfone has the general formula:

90 9 886/16 68

in which R _f , λ and y have the meanings given above "Y is a water atom or an aoyl group -CORf, in which Rf has the meaning given above" let and Y * is a hydrogen atom, an aoyl group of the formula -CORj. , as defined above, or a group of the formula -C _x H _2x NHY ₉ in which χ and Y have the meanings given above, 1st, where at least one of the groups Y and Y "is an aoyl group and at least one of the groups Y and Y * It can be made from a fluorine-containing carboxylic acid of the formula Rf-COOH, in which R _{f has} the meaning given above, or a derivative thereof, for example an ester, anhydride or acid halide, and a polyalkylenepolyamine of the general formula

in which χ and y have the meanings given above and E is a hydrogen atom or an aminoalkyl group of the general formula "C _x H _2x NH ₂ , In which χ has the meanings given above, 1st.

The polyalkylene polyamides, which are known compounds, can be straight chain or branched and can be used as individual compounds or as a mixture of isomers or a mixture of spanked polyamines with 3 to 6 nitrogen atoms can be used in the molecule. Examples of suitable polyamines are di-ethylene, di-n-propylene, Dl-isobutylene- and di-n-hexylene-triamine, TrlKthylen-, Trl-isopropylene- and TrI-n-hexylene-tetramine; 4- (2-aminoethyl) 1,4,7-triazaheptanj TetraKthylen-, Tetra-n-propylen-, Tetra-n-butylene- and tetra-n-hexylene-pentamine 4- (2-amino-ethyl) -1, 4,7-tetraazadeoane; and pentaethylene hexamine.

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The fluorine-containing carboxylic acids or carboxylic acid _{derivatives, in which R f has} a perfluoroalkyl group, and two times the perf1uorcarboxylic acid itself or its esters, anhydrides or acid halides, for example saturated straight-chain or branched-chain monocarboxylic acids or derivatives thereof with 4 to 6 to 14 preferred acid parts Molecule. They can be used as individual compounds or as solitary compounds with the specified carbon chain length in varying proportions. Examples are perfluorobutter, caproic, caprylic, laurine-f-ayrissic, palmitic and stearic acid and their isomers.

Those perfluoroarboxylic acids containing up to about 10 carbon atoms can easily be prepared by electrochemical fluorination of saturated aliphatic acids in anhydrous hydrogen fluoride and subsequent hydrolysis of the fluorinated acid fluorides formed, as described in US Pat. No. 2,567,011. ^v Ferfluorocarboxylic acids with a longer chain "ie those" which contain about 11 to 18 carbon atoms "can be obtained by reacting perfluoroalkyl iodides with oil with a sulfur trioxide content of about 15 to 45 $ at elevated temperatures and subsequent hydrolysis of the perfluoroarboxylic acid fluoride formed" as in French patent 1 342 60I described »can be obtained.

Those fluorine-containing carboxylic acids in which R _{f is} a group of the form

2 "

in which R, M, v, n, m and u have the meanings given above have "1st" can according to various described below.

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Procedure are obtained:

Those of these carboxylic acids and carboxylic acid derivatives in which ν «0, m is at least 1 and η + u is at least i, can be obtained from telomars of the formula s

in which R has the meaning given above, s and t

0 or integers from 1 to 20, β + t at least

1 is and E is bromine or iodine «can be obtained.

The manufacture of these telomeres is in the Belgian 714,162. For example, can these telomers by radical addition of polyfluorosoalkoxyalkyl halide telogens the formula

in which R and E have the meaning given above, unsaturated compounds which can be telomerized are obtained. The reaction can be initiated by worms or by a catalyst that initiates the formation of free radicals. The telogens can be obtained duroh reacting a corresponding fluorinated ketone with an ionizable fluoride, for example cesium fluoride _/ and reacting the fluorinated organic salt formed with a halogen other than fluorine or chlorine and tetrafluoroethylene, as in Belgian patent 687 649 and German patent application P. 15 68 059.8-42.

Those acids in which both ν as auoh η and u 0 and in which m is at least 2 can be prepared by using the above telomers in which t - 0, with iodoyanide or cyanide, preferably in excess,

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• ίο ·

and the nitr11 formed is hydrolyzed in a known manner to form the free SHure. The first reaction is expediently carried out under superatmospheric pressure of, for example, over about 20 to 200 atmospheres, at over about 30Ot. The hydrolysis may be with aqueous mineral acid, such as hydrochloric acid, phosphoric acid or sulfuric acid, carried out at about 60 to 125 C ^4.

Those acids in which m is at least 1, ν and u are equal to 0 and η is greater than 0, can be implemented by implementing of the above telomers in which t is greater than 0, with an alkali alloyanide and hydrolyzing the formed Nitriles with formation of the free acid, as described above «can be obtained. The implementation takes place preferably in aqueous-alcoholic solution at about 60 up to 100 ° C.

Those acids in which m is at least 1, ν - 0, u-1 and M is hydrogen, can be prepared by the above telomere, in which t is at least 1, with Sulfur dioxide with formation of the corresponding pyrosulfate or with oleum to form the corresponding hydrosulfate reacts, the pyrosulfate or hydrosulfate then with Reacts aqueous acid and the alcohol formed with Diohromat, Peraianganat or strong nitric acid the free acid is oxidized.

Those acids in which m is at least 1, ν and η both 0, u 1 and M fluorine 1 can be prepared. By doing one the above telomer, in the t ■ 0, with sulfur trioxide to the corresponding acid halides and halopyrosulfates, preferably fluoropyrosulfates, and the acid halides are halopyrosulfates, preferably Fluoropyrosulfate, then refluxed with water to

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BAD ORjQlNAL

dl · free acids. Those 8 acids in which v-1 and m, η and u «lie O Bind, can glelohen naoh dem Process from the above polyfluoro isoalkoxyalkyl halide telogens can be obtained.

Cures in which m - 1 and ν, η and u are all 0 can be converted from the above telegenes by reaction with an Orignard gene to the magnealum halide adduct "Utoaetien this adduct" with carbon dioxide and acidification of the ao obtained salt to form the Waken acid can be produced, as in the above-mentioned Belgian patent 687 649 be Bohr live. The Grignard reaction takes place rather roughly and can be carried out at temperatures considerably below CK.

The ester and acid halides of the above acids can be obtained from the acids by conventional methods.

The telomeres above and those derived therefrom fluorine-containing carboxylic acids and carboxylic acid derivatives can be prepared as individual compounds but generally in the form of bases of connections different chain lengths. Both the individual compounds and these mixtures are suitable for Manufacture of the fluorinated polyamides used for the manufacture of the new compounds according to the invention will.

The preparation of the above acids is in detail In Belgian patent 714-160.

If the groups R are perfluoroalkyl groups, then contain they preferably have 1 to 5 carbon atoms. If you Contain hydrogen, so is the atomic ratio

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Hydrogen fluoride at least lsi.

Preferably m is at least 1 and m + η 1 to 10. Examples of preferred groups of the formula (CFRg) ₂ CP-O-CP ₂ CP ₂ - are

CF,

F-C-O-CFg-CFg

FCO-CP ₂ -CF ₂ - «

CP,

CF.

FCO-CPg-CF ₂ -

F-C-O-CPg-CFg-

CF,

(Οίο)

CF,

PC-O-CP ₂ -CF ₂ -

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FC-O-CP ₂ CP ₂ =

(^ ^% - FC-CF,

PCO-CF ₀ CF ₀ - FC 0-CFoCF ₀ '

I f

(CP ₂ ) _g cp-j

CP ₃

That for the production of the new compounds according to the Fluorinated polyamide used in the invention can be produced by using the fluorinated carboxylic acid or the fluorine-containing carboxylic Mureder derivative with the polyalkylene polyamide, expediently in the molar ratio of polyamine to carboxylic acid or carboxylic acid derivative of about 1: 0.5 to 7 # at about 0 to 200% mixed together. In the best case, the Reaction take place in the presence of a suitable inert organic solvent. After completion of the implementation can the fluorinated polyamide can be isolated from the reaction mixture by known methods.

The fluorinated polyamide can be a single compound, a mixture of isomers of such a compound, or a Reaction mass of amides with two or more functional parts Be amld groups. It can be used without further cleaning

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the vinyl sulfone are converted to the divinyl sulfone adduct. OewUnsohtenfalle can of course also do it before the Implementation, for example by distillation or recrystallization, can be purified.

The divinyl sulfone adduct can be prepared by a suIfon with the fluorinated polyamide described above, expediently in a molar ratio of lsi to lOil. The reaction temperature and time depend on which fluorinated polyamide is reacted with which sulfon. The temperature can be in the range of 25 to 16CC « and the tent can be about half an hour to 4 hours. If desired, the reaction can be carried out in the presence of a inert organic solvent can be carried out. The divinyl sulfone adduct can by customary methods of the Reaction mixture are isolated.

The salts can be made by adding the Divinyl sulfone adduct with a salt of the heterocyclic tertiary amine with a salt-forming acid or, alternatively, the divinyl sulfone adduct with the heterocyclic one tertiary amine and the salt-forming acid mixed. These Reactions are preferably in the presence of an inert organic solvent carried out. The molar ratio of adduct to salt of the heterocyclic tertiary amine is preferably about 1 si to 1:15 *, preferably 1? 5 to IjIO. When the heterocyclic tertiary amine and the salt-forming acid are added separately, the heterocyclic tertiary amine, preferably in a slight excess, for example in an amount of about 1.1 to 1.8 moles of Aain per mole of acid are used. Reaction temperature and time depend on which divinylaulfone and which salt of a heterocyclic tertiary amine are used

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will. The temperature can be about 25Έ to 10 (K. and amounts to; preferably about 50 * C to 75 * C »and the Reaction time is about 5 minutes to 24 hours,

The reaction is preferably carried out in the presence of an inert one organic solvents or solvent mixtures, for example low-molecular allphatlecher ketones and alcohols. If a solvent is used it gives the maximum that can be used Temperature only from the reflux temperature of the reaction * - mixed. The implementation can take place at Uber Atmospheric Pressure be carried out »but is preferably carried out at AtmoBphürendruok.

If desired, the reaction in the presence of a tertiary aliphatic amine, for example triethylamine, which is preferably 1, or tripropylamine or tributylamine, be carried out as a catalyst. The amount of catalyst is preferably about 0.1 to 1.0 $, based on the weight of the reaction mixture.

After the reaction has ended, the salt can be removed by evaporation of the solvent or by cooling the reaction mixture * and Filter off the resulting product.

The salt obtained in this way can be used without further purification as Oil and water repellent agents can be used. But in the worst case it can of course be used before it is used, for example by recrystallization from an inert organic solvent such as acetonitrile, ethanol or saopropginol, which has been purified.

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The salts preferably have the formula

R _f - C - "H

-M -C-R,

Θ., Χ Θ

in which R _f , χ and y have the meanings given above »X is a halogen, preferably chlorine, 1st and R _f preferably have the form]

in which M and u have the meanings given above, m is an integer from 1 to 10, η - 0 or an integer from 1 to 10 and ed + η 1 to 10 has

The following examples illustrate the invention. example 1

49 g (0.475 mol) of DiMt hy lent riam in 60 ml of DiKt hy lather were in a reaction vessel with a dropper, condenser, Magnetic stirrer and calcium chloride drying tube in for 20 minutes Hiewasser cooled and then with stirring within 30 minutes with ^ 4.2 g (0.079 mol) of n-perfluorootanoyl chloride added. Then the reaction vessel was taken out of the water and stirring was continued at room temperature for 20 minutes. Then 100 ml of aqueous sodium hydroxide were added, and stirring was continued for 15 minutes. The educated gelatinous precipitate was made under reduced pressure

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filtered off and washed with water. Duroh consolation ^ in the air 31 g of i * 7-Bie "(perfluoroetanoyl) -l, 4,7" -tria; s & heptane as welflen solid, from P 94 to 97SJ, and the formula

0 0

η η

-C- NHCH ₂ CH ₂ NHCH ₂ Ch ₂ ! * !! - C -

obtain

2.4 g of this product were heated to 130 to IkCfC ^{in 15 ml of formamide until they had completely dissolved, and then heated to 14O 4} C for three hours with 2 ml of divinyl sulfone, cooled to room temperature and poured into a

Transfer funnel. 25 ml of water were added,

where there is a yellow water-based oil-free oily Sohioht formed, which extracted twice with 25 ml of diethyl ether each time became. The combined extracts were washed twice with 25 ml of water each time and dried over MgSO ^.

Duroh Evaporation of the ether in vacuo and recrystallization

the residue from carbon tetrachloride was 1,7-bis (perfluorootanoyl) -4- (2-vinylsulfonyl-ethyl) » ! »4,7-triazaheptane, F 93-94Έ, the formula

C ₇ F ₁₅ - C'- NHCH ₂ Ch ₂ NCH ₂ CH ₂ NH - C - C ₇ F ₁₅ CH ₂ CH ₂ SO ₂ CH-CH ₂

obtain.

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15 # 18 g (0 * 015 mol) of this product in 50 ml of acetone were added with 5 drops of triethylamine as a catalyst and then dropwise with 8.28 g (0.1 mol) of pyridine, 5.04 ml of 12N hydrochloric acid and 10 ml Ethanol added. The mixture was stirred, refluxed for> hours and cooled in an ice bath for 1 hour, 18 g of crude product separated out. This product was filtered off, washed with diethyl ether and recrystallized from acetonitrile, with 10 g of 7-bis "(perfluorooctane-3 rl >> ^t 1- [2- (2-pyrldinlumXthyl <»eulfonyl) ~ ethyl] ~ 1,47-trlazaheptane-ohlorid, yield 64 °, P 172 to 174 ° C, were obtained.

Calculated for

Found t

iC 30.8 #; H 2.06; N 4.96; P 51.0; S 2.84; Cl 3.14;

C 30.59 *; H 1.88; N 4.95 / P 49.69; S 2.94; Cl 3.49;

The infrared spectrum of the product (KBr) shows bands at about 3.0μ (medium strength), 2.45μ (weak), 5.9μ (strong), β, ΙΙμ (weak), 6.5μ (medium), 7.55μ (sohwaoh), 7 «75μ (medium strength) and an envelope of strong bands at around 8.1 to 8.9μ. Formula"

P «- -C-NH

C ₇ P ₁₅

CH ₂ CH ₂ -N-CH ₂ CH ₂ -NH-C-

C ₇ F ₁₅

.Cl

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The product can be dispersed in water.

This chloride has an unusually high surface area and can in the usual manner for surface-active agents, for example for the production of emulsions and to increase the network capacity, for example for «FXrben from Textile fiber materials, can be used «to influence it the surface tension of water was measured with a Tenslo meter according to ASTM test D-1590. The results were «

Concentration of Gbsrflttohen- Connection in water tension

Qew.-g dyn / om

ItO 19 * 5

0.5 S0, l

0.1 25.5

When this product is applied to the "in * B microscope" by "evaporating to a dilute aqueous solution", a drop of water applied to the surface forms a contact angle of 75 ° and a drop of mineral oil ("Nujol * Saybolt viscosity 560/590 at 58 ⁴ C, specific owioht 0.880 / 0.900 at 15.5 * 0 a contact angle of 85 °. One drop of the same mineral oil forms a contact angle of about 25 on a slide treated with acetone alone, 5 °.

Example 2

20 g (0.0467 mol) of methyl n * perfluorootanoate in 25 ml

Diethyl ether and 5.4 g (0.0255 mol) triethylenetetramine

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were refluxed for 2k hours. By evaporation of the solvent under reduced pressure, 20 g of a white, sticky solid material, from which by Uekrlatalllaleren also acetonitrile l, 10-BI * - (perfluorootanoyl)! «4,7,10-tetraasadeoan in the form of welfien powder from F 89 bia 92 ° and the Forneli

0 0

H ft

C ₇ F ₁₅ - C - OTCH ₂ CH ₂ NHCH ₂ CH ₂ MHCH ₂ C ^ nH - C - C ₇ F ₁₅

was obtained.

6 "g of this t roduktes were dissolved in 20 ml dimethylformamide by heating the mixture a few minutes to 80 ¹ C and the solution was heated for 3 hours at 90t with 3 ml Divinylaulfon. A wei6er solid was filled by addition of 20 ml of water, then washing with water and drying in air, 1.10-Bi- (perfluorootanoyl) -4,7-bis- (2-vinylsulfonylethyl) -1,4,7,10-tetra «azadeaan from F 118 bis and the formula

C ₇ F ₁₅ -C-. NH (CH ₂ CH ₂ M) ₂ CH ₂ Ch ₂ NH - C- - C ₇ F ₁₅ CH ₂ CH ₂ SO ₂ CA-CH ₂

revealed.

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31 * 95 β (Ο »03 mol) of this product in 135 ml of acetone were treated with 8 drops of triethylamine as a catalyst and then with 31 * 64 g (0.4 mol) of pyridine, 19.5 tnl of 12N hydrochloric acid and 20 ml of ethanol. The mixture was boiled with stirring for 3 hours in the reflux and then cooled in an ice bath for one hour, during which the raw product precipitated. By filtering off this product and ötakflstallieiespen from Aoetonü. ο? 4βη 15 g of product from P 160 to 165 ⁰ C obtained. By recrystallizing twice more from acetonitrile, water-soluble l, 10-bis (parfluor <-

1,4,7,10-tetraazadeean dichloride from F 170 bis obtain.

Example 3

5 * 0 g (0.0049 mol) 1.7 ° Bi8- (perfluoro (7-oxa-8Hnethylnonanoyl)] - 1,4,7-triazaheptane and 5.8 g (0.049 mol) divinyl sulfone in 35 ml dimethylformamide were Stirred at 75% for 4 hours, cooled to ambient temperature and diluted with 70 ml of cold water, whereby 3.6 g of crude product precipitated. Purified 1,7-bis- [perfluoro- (7-oxa-8- aethylnonanoyl)] - 4 (2-vinyl-8ulfonylXthyl) -l, 4 _J-7 trlazaheptan P 94.5 to 95 * 5% and the Formels

j ₅ N -C ₂ H ₄ SO ₂ CH-CH ₂

obtain.

Following the procedure of Example 1, this product was reacted with pyridine hydrochloride to give water-soluble

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[(CP ₃ ) gCP0 - (CP ₂ ) ₅ - CONHCH ₂ CH ₂ J ₂ N -

to

.Cl

was obtained.

BelapleH 4 to 24

According to the procedure of the above Beleplele, the following became further connections established 1

[CP ₃ (CF ₂ ) ₄ - C - MHCgH ₄ I ₂ M - C ₂ H ₄ SO ₃ C ₂ H ₄ SOgCgH ₄ -

. KSO ₁

duroh implement from

-C- MHC ₂ H ₄ J ₂ M - C ₂ H ₄ SO ₂ C ₂ H ₄ SO ₂ CH - CH ₂

with 2-methylpyrldine hydrogen sulfate

[PC-CP ₂ (CP ₂ ) ₂ -C- MHC ₂ H ₄ J ₂ M CF,

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1338544

CP,

duroh implementation of

[PC- CP ₂ (CPg) ₈ - C - NHCgH ₄ JgIi -

CP-,

with 3-methylpyridine-hydro, iodide

CP ₃
β »

. Cl

by unsetting from

CP ₃ O

1 β

- CHgCHgSOgCH-CHg

CF-

with ^ -Methylpyridin-Hydroohiorid

ICP ₃ (CFg) ₁₂ - C

CH ₃

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by implementing

iCP ₅ (CF ₂ ) ₁₂ - C - HHC ₂ H ₄ J ₂ N -

Bit 2,6-DlJB «thylpyri <lin hydrofluoride

.Br

by bidding from

-C- 1IHC ₂ H ₄ J ₂ H-

nit 3 "5-2> ln" thyIpyridln-hydrobroiBld

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C - NH (C ₂ H _n N) ₂ C ₂ H ₄ NH - C CHCH ₂ SO ₂ CH ₂ CH

CH

₃ CH ₃

.SO.

0 η

by inaccessibility of

If

CF ₃ (CF ₂ ) ₇ -C - NH (C ₂ H ₄ N) ₂ C ₂ H ₄ NH-C- (CFg) ₇ CF CHCH ₂ SO ₂ CH - CH

with 2,3-dimethylpyridine sulfate

CF _{3 0}

W.

H ι «t 9 * 5

CF ₃ (CP ₂ CF) ₃ CF ₂ -C-NH (C ₂ H ₄ N) ₂ C ₂ H ₄ NC-CP ₂ (CF ₂ CF) ₃ Cf ₃

.2H ₂ PO ₄

909 886/1668

by Ura »« etching of

H 0

ι η

- C - NK (CgH ₄ M) ₂ C ₈ H ₄ M - C - CF ₂ (CF ₂ CF) ₃ CF ₃

CH ₂ CH ₂ SO ₂ CH-CH ₂

with 2,4-Dimethylpyridln-dihydrogtnphoephät

HO

- C - MH (C ₂ H ₄ N) ₃ C ₂ H ₄ H -C- (CFg) ₇ CF ₃

CH ₂ CHgS

■ 43

duroh Uaaetz «n of

CF ₃ (CFg]

SO ₂ CH-CH ₂

with 2,4,6-triujethylpyridine-phoephmt

988 6/166 8

CF

CF,

CH ₂ CH ₂ SOgCH ₂ CHg

through unset win from * ιΘ

-C- HH (CgH ₄ H) ₃ -CgH ₄ IIH - C CF,

CF,

nit

- C - HHC ₂ H ₄ - H - CgH ₄ HH - C -

909886/16

.ClO

duroh lfoetts «n of

C -

ti

• C -

Bit 2,?, 4,6-TetreiB «thylpyrldln-hydroblond

CF

CF,

CF-,

CB ₂ CH ₂ SO ₂ CH ₂ CB ₂ -

duroh

from

CF, 0

t '"■ η

FC-CP ₂ (CF ₂ ) ₂ - C O • C -

CF

CH ₂ CH ₂ SOgCH-CH ₂

909886/1668

It 2, J # * # 5 "6-Pent" inethylpyridine-hydrobPomid

» R

CH ₂ CH ₂ SO ₂ CH ₂ CH -

duroh unietsen from

.ClO

CH ₂ CH ₂ HH ₂

CH ₂ GH ₂ SO ₂ CH-GH ₂

with quinoline hydrochloride

CH ₂ CH ₂ MH ₂

.ClO

909886/1668

duroh um ·· t sen from

CHgCHgSOgCK-CH ₂ 0 MH ^ CHgCH ₂ -M-CHgCHg-H-CH ₂ CH ₂ M-CH ₂ CH ₂ -MH-C

CHgCHgNHg CHgCHgSOgCH-CHg

■ it Pyrldln-hydroohlorld

O CHgCHg-HH-C- (CFg) ₆ CF ₅

CHgCHgSO ₂ CHgCH ₂ -

CU,

duroh UetetMn of

-M-CH ₂ CH ₂ -M-CH ₂ CH ₂ -JIH - (^ CH ₂ -t
CHgCH ₂ SOgCH-CHg

With 2-methylpyridylnhydrol) ro “id

90 9 886/1668

dureh HmMtMn from

CE- CB,

! «Θ

linset Mn from

nit 2 "?" 4, S "6-Ptnt" methylp7ridine hard freeze chloride

.Cl

909886/166 8

by tfos «tsen of

Bit Pyrldln hydrochloride

.BrO

duroh \ Jms * tz9n from

with 2-methylpyrldine hydrobromide

duroh Uoeetsen by

909886/1668

■ It Chlnolin-hydroohlorld

C!

duroh implement from

CHgCEgSOgCE-CH ₂

■ with 4-methyl pyridine dihydrogen phosphate

O H

H ·

HO

C ₇ F ₁₅ -CM- (CEgCBg-M) ₅ -CE ₂ CEg-MCC ₇ P ₁₅

CH ₂ *

.5ClG

duroh

from

O H

C ₇ F ₁₅ - C - M - (CEgCE ₂ -M), - CEgCE ₂ H O tn MC

909886/166

with pyridine hydrochloride

HO

t R

-M-C-

C ₇ F ₁₅

CHgCHgSO ₂ CH ₂ CH ₂ -!

duroh start of

H
t

CHgCH ₂ CH ₂ - N - CHgCHgCH ₂ - M

CH ₂ CH ₂ SO ₂ CH-CH _{2 with} pyridine hydrochloride

m C

-C ₇ P ₁₅

CBgCHg-MH-CHgCBgSOgCB-CBg CHgCHgSO ₂ CH ₂ CH ₂ ^ M, CH ₂ CH ₂ -NH-C- (CPg) ₆ CP ₃

m
0

9 0 9 8 8 6/1668

by ftasetsen from

old pysldine hydrochloride

sows fluorinated quarters a ^ soniisfisalse. 0mMS the Ei-fIMung kfSsmen ves ^ endfifc ^ © Mdn, un paper and natQfliohe and s ^ nth®tiffi3he ^ oJctilfaa ^ .- t us-eriaiian ,, elneohlieSlieh Baus · * Nylon, wool »PoIyHt ^ Iant» r * phth * Xat and PoIy ^ oryl-

and iBBbesond «» i 0 ^^ © b® and Faeevn made of cellulose
indicated Celluloaedexlvsi ^ tSigi; nl® BauetfoXle, Lelntn,

vezseiftei Ü ^ iluloseaeetafc and Salse von 81 «uad wass @ ralW9ieend eu faaohen. she
can also be made of stature and / or synthetic fibers »for example oils of polyethylene terephthalate,

909886/1668

Polyacrylonitrile, nylon, cotton and wool will. If desired, aids, For example, those that make a fabric crease-proof or enable the embossing of patterns or a softer one Lend grip, be applied. Besides, you can too other materials, such as surfaces made of wood, plastics, Qlas and metals to be treated with these salts.

The salts can be applied to the article to be treated from a solution or dispersion and the solution or dispersion then evaporated. If necessary, the object treated in this way can then be cured at an elevated temperature. The amount of oil and water repellant agent can be in the range of about $ 0.5 to $ 20, based on the weight of the article being treated, and is preferably from £ 1.0 to £ 10.0. Since the salts are soluble or dispersible in water, they are preferably applied from an aqueous solution or an aqueous dispersion. Unusually any organic liquid, for example acetone, methyl ethyl ketone, acetonitrile or dimethylformamide, which is inert to the object to be treated and which is able to dissolve or disperse the required amount of the agent, can of course also be used.

Evaporation of the solution or dispersion can be done by drying in air at room temperature · If the the treated object is to be hardened, the evaporation can take place before or during the hardening. Preferably it takes place before hardening for a sufficient time to evaporate the solution or dispersion to dryness, after which the object is at 100% to 16ö «C for a time which is the shorter «the higher the temperature, and in that.

909886/1668

Range from about 1 second to 5 minutes is »hardened will.

The salts according to the invention are applied to cellulose textile materials from an aqueous solution or dispersion and in the presence of a catalyst such as is usually used as a crosslinking catalyst for crosslinking plastics with cellulose materials. The salts can be used together with both basic and acidic catalysts and therefore have the advantage that they can also be used together with an embossing of patterns in the textiles "which is usually done using acidic reagents and / or catalysts". The cellulose textile material is moistened with an aqueous solution of the catalyst, air-dried "in order to separate off excess water and then impregnated with the aqueous solution or dispersion" by immersing it in it for a period of normally 30 seconds to about 30 minutes "so that it about 1 to 20 pounds, preferably 2 to 8 pounds of the salt, based on the woven fabric, absorbs. The material impregnated in this way is then ^{heated to 100 to 165 8} C for a tent "which is the lower" the higher the temperature is "and is in the range of about 15 minutes to 30 seconds". After the reaction of the salt with the cellulose textile material has ended, the chemically modified cellulose textile material is washed free of excess catalyst with water and dried.

Alternatively, the cellulosic fabric can first be treated with a aqueous solution or dispersion of the fluorinated quaternary Ammonium salt impregnated according to the invention "then treated with an aqueous solution of the catalyst"

909 8 86/1668

air dried and finally heated and the salt to implement with the cellulose material. According to another The catalyst is modified with the aqueous solution or dispersion of the salt mixed, and the cellulosic textile material bit is impregnated in this mixture,

The cellulosic material can be of ohemiaohan modification

also under Wassarauasoiiluß, for example in presence of solvents which penetrate cellulose fibers, such as benzene, chloroform, dioxane and acetone.

The base catalyst should generally be a Association constant in water of at least 1.8 χ 10 "^ at 2515 have. Examples of suitable base catalysts are phosphates, carbonates and hydroxides of alkali metals, such as sodium phosphate, carbonate and hydroxide, and Potash Hydroxide? Brdalkalihydroxyde, insohlieeiioh Caloiumhydroxyd and Magnealuahydroxydf and quarternVre Amnonlumhydroxyde, such as tetraethyl and benzyltrimethyl ajntionium hydroxide. Suitable acidic catalysts are the mineral muds and strong organic cures, as well as the ammonium salts, Amine salts and metal salts of strong acids. Preferably the salts of strong acids, for example ammonium chloride, magnesium chloride, zinc nitrate and zinc carbonate used. The catalyst concentration usually depends on the strength of the acid or base, the unaccustomed reaction rate and the type of treatment to be treated Cellulosic material and is generally about 1 to 20 pounds, preferably 2 to 5 pounds based on the weight the solution.

9 0 9886/1668

. ₅₉ - 193854A

The pruning of textiles for oil repellency is described in Textil · Research Journal, April 1962, pp. 322-4 · It consists in the careful use of drops of geelsehen of a mineral oil ("Nujol") and n-heptane in varying proportions on the treated tissue applies. The drops are left on the tissue for three minutes, after which it is determined visually whether they have penetrated or wetted the tissue. The essence of the gene with the highest beptane content that niofat penetrates into the tissue or has it is the oil repellency value of the tissue (see Table X).

9098 86/166

193854A

Tabel Olabwelsunga- volume £ at SOi; at Volua- £ at

worth ffujol (Saybolt viscosity at 20Ji an η-Hep tan

360/590 at 38 * y «pezifi- (Kp 98-99 * C) see * weight 0.880 / 0.900 at 15.5 *)

150 0 100

140 10 90

130 20 80

120 30 70

110 40 60

100 50 50

90 60 40

80 70 30

70 80 20

60 90 10

50 100 0

0 no Mliieralula deviation

When typical grease stains result in materials on dripped a tissue and dabbed the bottom with blotting paper those tissues with an ul rejection value of 50 to 70 prove to be only KKSIg FleekenbeetKandig, those not having an oil value of to 90 as well fleokenbeetXndlg and those old Olabweieunga values of 100 and above as excellent fleekenbestlbidig.

The hydrophobicity of the treated fabrics was determined according to KS Method 22 * 1961 of the "American Association of Textile Chemists

909886/166 8

and Colorists ", (cf. Teehnloal Manual and Yearbook of this Association, pp. 152 to 153). It should be noted that this method does not interpolate the six "standard spray test values", ie 0, 50, 70, 80, 90 and 100, provides.

The washfastness of the treated fabrics was determined by doing this repeatedly in a household wash washed with an all-purpose potato in pure water and then dried in a household dry masohine and ironed before the exam.

For the tests, 4% aqueous 1,7-bis- (perfluorooctanoyl) -4-2- (2-pyridiniumthyisulfonyl) -thyl J-4,7-trlasaheptane-chloride was used. The solution remained cloudy even when heated to 60 ° C. Weighed samples of cotton printed matter (80 χ 80 counties preconditioned at 50 # relative humidity) were placed in aqueous catalyst solutions containing 5% sodium hydroxide (sample a), 5% magnesium chloride (sample b) and 5% sodium acetate (sample c) for three minutes immersed. the swatches were wrung, immersed for 10 minutes at 85 * C dried 10 minutes in one of the portions of the LSsung of the oil-repellency agent, then dried! cured for 10 minutes at 851 and 5 minutes at 150 ⁰ C. Thereafter, they were carefully into Rinsed in cold water, dried again for 10 minutes at B&K , ironed and conditioned at 50 ° relative VeuahtiidMit.

ua fQe $ ssu8t rush

iver VeuahtiidMit ua fQe $ ssu8t rush * The specimens were again "weighed" close to the mean they picked up and were subjected to oil and water repellency tests. After every wash and prior to the bottom test, the swatches were ironed again and conditioned at 50 # relative humidity. The results are shown in Table ZX.

909886/1868

i 1

in in

O OO

V4 «Ί V4

OOO

«Η« * f * 4 <M «· < > 4

OOO * - («- (« - · OOO

* - <* H Vl

OOO OOO

«H w-f * ·«

OOO

r?

ΙΛ O

8 86/1668

When treating paper, the salsa according to the invention can either be applied to the paper from outside, for example by treating the paper with a solution or dispersion of the grease and then inoculating the solution or dispersion as described above, or the salts can be removed Paper stock sugeeetst w @ rden »before it is deformed. If the paper is made UV- and water-repellent for the latter treatment, then the salts will swedeeftSig in © in®? Amount of about 0.2 to $$ » preferably 0.5 to 2 $, based on the dry weight, Bugaaetst · The S & is can translate the fabric as such across in the form @@ imr. I & eiatg © the suspension in water © the one®si of the other @ b®n ^ called solutions or dispersions ^ ittel awg @ s @% st

Gewünsohtenfall8 can && ß BmIz

Paper stock zueasaaien nit asid®r®n Hblieli @ n Αιββ ^ Ξφα «wi® fillers, beiaplel8K®iiS® kaolin, ka © liB ₉ © sl © iw“ oarbonate or titandio ^ fäg
Hydrocarbon @ d © f Mafeisyteeetee HafeiifipssaiLs Sfei ^ k® ^ Casein, Asphaltesiuleion®gb

Alum, added

Paper 1st in
MlBliig and

C. Oil

It says ύ & Β siaa Tmpi®n of castor oil, toluene and ivy ^ a applies to the paper in varying degrees. The fropf @ n 15 seconds on deai Faples? gal & e ^ en, after which it is determined whether si © in the paper @ inge ^ Fwig @ ii

90 9 886/1668

or have wetted ee. Let us recognize Dee Sindringen " that the paper has become dark. Darkness itself a small portion of the flee under the drops is to be regarded as Sindringen. "The number of the glacier with dea highest heptane content / that still penetrates the paper or it wets «is the" kit number "of the paper and as look at the oil degradation value of the paper (see table ΙΣΖ).

T a b e 1 1 e III

^ Kit number Volume castor oil Volume toluene Volume heptane

O 10 20 30 40 50 60 70 80 90

100

1 200 0 2 180 10 3 160 20th 140 30th 5 120 40 6th 100 50 7th 80 60 8th 60 70 9 40 80 10 20th 90 11th 0 100 12th 0 90

Papers With a kit number of about 5 to 6 or less

are only “JtSig” oil-repellent. Papers with kit numbers from 8 to 10 and above are good bsw. excellent oil-repellent.

909886/1668

Hand sheets made of unsized paper made from hardwood / white wood 50/50, treated in whip up to 400 according to Canadian Standard Freeness "were" with 4% aqueous 1,7-bis- (perfluoroetanoyl) -4-C2- (2-pyridiniunethylsulf onyl) ethyl] -1,4,7-triazaheptane by immersing them in it for one minute, then removing them, dabbing the excess solution with blotting paper and drying the leaves on a laboratory dryer for 1½ minutes at 115% and 72 hours at 72K and 50 $ relative humidity conditioned ·. They were then subjected to the oil repellency test described above. They had kit numbers from 9 to 10, so they had excellent oil repellency.

12 g of bleached Kraft paper stock from a "Bartholz / Weiohholz" Oemlsoh 50/50, treated in the server up to 70 seconds Williams Preeness, were in a "Waring" (T.M.) - Mlsoher, 5 seconds at low speed and then 15 seconds at high speed in 500 ml of water dispersed in a homogeneous slurry. This slurry was diluted to a consistency of $ 0.405. WKS rl ge Solutions with varying amounts of i, 7-bis (perfluorootanoyl) -4- [2- (2 * pyridiniumethylsulf onyl) ethyl] -1,4,7-t riazaheptane were added; and the slurry became slow stirred to uniformly distribute the solution of the salt in the slurry, and then into three equal parts divided, each of which is diluted to a consistency of $ 0.05 and in a Wiilians porm to form handsheets was deformed by 19 x 19 <* m. These sheets were made with Pressed to a consistency of about 32 pounds in a Noble and Wood press and then in a Foal and Wood rotary dryer Dried 11/2 minutes at 115 ^ 5. The oil rejection the sheets produced in this way were immediately after drying and again after 2 4-st and ige r aging at 72 * D and 50Jf relative humidity determined · The results are compiled in Table IV.

909 8 86/1668

tab Amount of funds hurry IV To in the Auf eehlaOmmg « ■ Kit number ¹¹ dry $ dee Trookeneewlohta 2 0.1 5 0.2 6th 0.5 8th 0.5 0.6 9 0.7 10 0.9 10 1.1

Aged for 24 hours

5 7

12th

When harvesting textiles and paper with other fluorinated quartz Airaoniiraealsen be treated according to the invention, as described above, the same results are obtained, i.e. the salts impart good properties to these materials olive whitening,

909886/1668

Claims (6)

Godfather to s ρ pll ehe 1. Fluorinated quaternary ammonium salt of the alXgene genes Formula O
η ■ Θ in the R _f one ferfluoroaltcyl group salt 3 to 17 carbon atoms or a group of the general formula In which each of the groups "they can be the same as mer, is a fluorine atom or a PluoMllqrlgruppe with up to $ carbon atoms, or 2 of the groups R" ufiajmnen form a pluoroalkyl group with up to 18 carbon atoms "where at least one of the groups R © in Fltioratom is "ü and v" all can be the same or different, are 0 or 1, m and n, which can be the same or different, are 0 or integers from 1 to 20; where m -f η 0 to 20 is, ta at least 1 let, Kenn ν gleloh 0 and ν 0, if m + η * u is greater than 0 ι M is a hydrogen or fluorine atom, namely a hydrogen atom , if η is greater than 0 let, istι 909886/1668 χ an integer from 2 to 6, preferably from 2 to 4 ietj y an integer from 1 to 4 ietj Z is a hydrogen atom, an aoyl group of the formula -CO-R ^, in which R _{f has} the meaning given above, a vinyl sulfone group of the formula in which ρ is 0 or 1 »each of the groups R, which can be the same or different, is a hydrogen atom or an alkyl» or substituted or non-substituted aryl group and Ir is an alkylene, arylene or aralkylene group; or a residue of an adduct of a suIfon and a tertiary amine de ^ formis -CHR ² = CHR ² -S0 ₂ - (R- ⁵ SO ₂ ) -CHR ² «OHR ² -N in which R, fr and ρ have the meaning given above and "N ^) is a pyridyl, quinolinyl or mathyl-substituted pyridyl group, ietj Z is a Wasserstoffaton, a Aoylgruppe the formula -CO-Rj., As defined above, a vinylsulfone group, as defined above, a residue of an adduct "of a sulfone and a tertlMren amine as defined above, or a group of the formula -C _x H _2x -NH-Z, in which χ and Z have the meanings given above, where the groups Z ¹ , when y is greater than 1, can be identical or different; X is a halogen, Sulphate, hydrogen sulphate, phosphate or hydrogen phosphate ion is; q is an integer from 1 to 4 equal to the number of adduct groups Sulfon / tert IMr is amine in the salt; and 909886/1868 r is an integer from 1 to 3 equal to the valence of the Is anion; with the proviso that the salt has at least one acyl group of Formula -CO-Rj, and at least one adduct group sulfone / tertiXr Contains amine. 2. Salt naoh claim 1, characterized in that Z is a residue of an adduct «one Sulphones and a tertiary amine of Claim 1 given definition, in which all groups R are hydrogen atoms are, ρ «O and N) is a pyridyl group and Z is an acyl group as defined in claim 1 1st. 3 .. Salt naoh claim 1 or 2, characterized in » that R ^ is a perfluoroalkyl group with 6 to 14 carbon atoms »preferably a perfluoroheptyl group» is. 4. SaIs naoh claim 1 or 2 »thereby g β ke nnzeiohnet that R _{f is} a group of general failure« is, in the m, n, u and M indicated in claim 1 Have meaning and preferably η 1 to 10 and η 0 to is, 'where D + nl to 10 »is. 5 «Fluorinated quaternary ammonium salt of the formula} 909886/166 8 C ₇ P ₁₅ 0
il
- C H
_1 HO
-CH ₂ CHg-M-CHgCHg -HC- ^ _ ©
.c: CHgCHgSO ₂ CHgCHg-M ^ or Vw 0
-I. R.
-M H
- \ VJlgVSl ~ —If / a - VMnwQn - il 0
- "- Vw- CHgCHgSOgCH ₂ CHg-M 4M or O H -C- H 0 I 11 -M-C or OH Pe * -C-M- - CH ₂ CH ₂ HO - M - C - C ₇ P ₁₅ ΘΘ 909 8 8 6/1663 ίΘ 6. A method for producing a salt according to any one of the preceding claims, characterized in that that one has a divinyl sulfone adduct general formula in which R _f * χ and y have the meaning given in Claim 1; Q is a hydrogen atom, an aoyl group of the formula as defined in claim 1, or a vinyl sulfone group as defined in claim 1, | and Q is a hydrogen atom, an acyl group of the formula -CO-R ^ l a vinyl sulfone group as defined in claim 1, or a group of the formula - C _x H _2x -MHQ, in which χ has the meaning given in Claim 1 and Q has the meaning given above * let; with the proviso that the vinyl sulfone adduct contains at least one acyl group of the formula -CO-R- and at least one vinyl sulfone group with a salt of a heterocyclic tertiary amine, namely a halide, 90988671668 Sulfate or sulfate of pyridine, quinoline or a methylsubstit uirjrien pyridine converts, the salt dea heterocyclic tertiary amine is preferably formed in situ. 7- Use of a salt according to any one of the claims 1 to 5 # around an object such as paper or to make a textile, ÖJL «and / or water-repellent, SQ-9886/1668 bad ORIGINAL