CH628247A5 - Aqueous, film-forming concentrates for extinguishing or preventing fire with a content of non-anionic compounds containing perfluoroalkylalkylenethio groups - Google Patents

Description

65 The present invention relates to new, aqueous, film-forming concentrates for fire extinguishing or fire prevention containing non-anionic perfluoroalkylalkylene thio group-containing compounds which have surfactant properties.

628 247

4th

have ter. The importance of surfactants is that they. can act as wetting agents, emulsifiers, solubilizers and / or dispersants. Although surfactants have been produced from many classes of compounds, perfluoroalkyl groups (Rf) containing surfactants have recently become known. Rf-substituted surfactants are particularly valuable because they are known to lower the surface tension of liquids more than any other surfactant. For example, surface tension in water of less than 17 dynes / cm can be obtained with fluorinated surfactants, while non-fluorinated hydrocarbon analogs only reduce the surface tension of water to about 30 dynes / cm. For this reason, fluorinated surfactants have been used in fields as diverse as emulsion polymerizations, self-polishing floor waxes, electroplating, corrosion inhibitors, paints and fire-fighting agents.

Various fluorinated, amphoteric and cationic surfactants are known from US Pat. Nos. 2,764,602.3,555,089 and 3,681,413 and German Offenlegungsschriften 2,120,868, 2,127,232,216,57 and 2,315,326. The fluorinated compounds used according to the invention, however, differ significantly from the known compounds.

Intermediates which are suitable for the preparation of the surfactants are described in US Pat. No. 3,471,518, which describes the addition of Rralkylenethiols to maleic acid and maleinates, and in US Pat. No. 3,706,787, which describes the adducts of RrThiolen with dialkyl and monoalkylmaleinates are described. German Offenlegungsschrift 2 219 642 discloses RrAlkylenthiolangerung products with dialkylaminoalkyl acrylates and meth-acrylates; these compounds are cationic surfactants and have no 1,2-dicarboxylic acid content. While all fluorinated amphoteric surfactants of the prior art are synthesized by quaternization of a corresponding tertiary amine with an alkylating agent, such as lactones, sultones or halogenated acids, the amphoteric surfactants used according to the invention are prepared by a simple ring-opening reaction without the use of possibly carcinogenic alkylating agents forth. The surfactants used according to the invention are excellent wetting agents, especially when used in combination with other fluorinated and non-fluorinated surfactants. Furthermore, they can be manufactured much more economically and safely.

The present invention relates to aqueous, film-forming concentrates for extinguishing or preventing fire by suppressing the evaporation of combustible liquids, characterized in that they

(A) 0.5 to 25% by weight of a non-anionic fluorinated compound of the formula

Substance atoms, alkyleneoxyalkylene with 2 to 12 carbon atoms or alkyleneiminoalkylene with 2 to 12 carbon atoms, in which the nitrogen atom contains hydrogen or alkyl with 1 to 6 carbon atoms as third substituent,

5 y 1 or zero,

X is oxygen or NR, where R is hydrogen, lower alkyl having 1 to 6 carbon atoms or hydroxyalkyl having 1 to 6 carbon atoms, or X together with Q forms a piperazine ring, and 10 Q is a nitrogen-containing group with the formulas

R3

(la) - (R2) k-N ^

R4

; r3

(lb) - (R2) k-N - ^ - R5 A® and NR4

R3

20 (lc) - (R2) k-N - ^ - G®

\ R4

represents what

R2 is linear or branched alkylene with 2 to 12 carbon atoms, linear or branched alkylene interrupted by oxygen or sulfur with up to 60 carbon atoms or hydroxyl-substituted alkylene, where R2 is preferably straight-chain or branched alkylene with 2 to 5 carbon atoms, and

30th

35

40

k is 1 or zero, with the restriction that k is 1 when X is oxygen,

R3 and R4 independently of one another each represent hydrogen, an alkyl group or substituted alkyl group having 1 to 20 carbon atoms, a phenyl group, an alkyl- or halogen-substituted phenyl group having 6 to 20 carbon atoms or a polyethoxy or polypropoxy group with 2 to 20 alkoxy are units, with the restriction that R3 and R4 are not hydrogen when X is oxygen, and wherein alkyl having 1 to 5 carbon atoms, dienyl, hydroxyl, carboxyl, halogen, alkylene dialkylphosphonate such as methylene diethylphosphonate or a group of the formula

45 _N

\

R3

R4

(I) Rr-R, -S- (CH2) y-CH - COO®

©

CH2-COX-QH, (II) R [-R1-S- (CH2) y-CH-COX -QH

ch2-coo®

and (III) Rf-R1-s- (ch2) -ch-c

o are suitable as substituents on alkyl and methyl, halogen or hydroxyl as substituents on phenyl and R3 and R4 are preferably alkyl with 1 to 4 carbons, A® is an anion which forms an ammonium salt of the formula NH4® A® and is derived from alkyl halides, benzene or chlorobenzenesulfonate esters from alkyl alcohols and methyl and ethyl sulfates, where Ä® is preferably CL®, BR®, CH3CH20S03® 55 or CH30S03Q, R5 is hydrogen, alkyl or hydroxyalkyl, aralkyl or a group of the formula - Is (CH2) n-COO-alkyl, in which alkyl contains 1 to 18 carbon atoms, and R5 is preferably methyl, ethyl, propyl, butyl or benzyl, and

"N-Q

CH2-C

%

O,

wherein Rf straight-chain or branched perfluoroalkyl having 1 to 18 carbon atoms or such a perfluoroalkyl substituted by perfluoroalkoxy having 2 to 6 carbon atoms, R1 branched or straight-chain alkylene having 1 to 12 carbon atoms, alkylene thioalkylene having 2 to 12 carbon atoms

60

65

G ° a group of the formula

- (CH2) n-COO®; - (CH2) 3S03®;

-CH-COO® or -C-COO® is I 'II

CH2-COOH CH-COOH

what is ibis5;

Q is also a cyclic amino group of the formulas

5

628 247

(2a)

(2 B)

-R2-N ^ Y

2nd

• R -N / Y

(4b)

- (R2).

Za

> W

and

(2c)

U

R "

-R -N Y

V V © a e

'.5

R "

10th

Za

(4c) - (R)

4— Il '•

II

•. •

and is what

Y is a remainder of the formulas

- (CH2) 4-, - (CH2) 5-, - (CH2) 2-0- (CH2) 2-and - (CH2) -CH-N- (CH2) 2-I I R7 R8

is in which R2, RS, A® and G® have the meanings given, and

R7 and R8 independently represent hydrogen or a lower alkyl or hydroxy lower alkyl group having 1 to 6 carbon atoms, with the restriction that R8 is not hydrogen when X is oxygen;

Q is also an aromatic amino group of the formulas

G 0

wherein

20 Z is halogen or methyl and (a + b) is an integer from 0-3;

or a heterocyclic amino group of the formula

(3a)

Za

Za

©

(3b)

(3c)

V 0

R "

# Za

2 S> S

S |

V- /

and

N ©

i ©

a ring-fused aromatic amino group of the formulas

(4a)

Za

- (E2).

Eg

^ V

(5a) - (R2) k-E 25 (5b) - (R2) k-E®-Rs A®

(5c) - (R2) k-E®G®

is

where k is one or zero and

E is N-hydroxyalkyl- or N-aminoalkyl-substituted pyr-30-rolyl, pyrazolyl, imidazolyl, triazolyl, indolyl or indazolyl or py-ridazinyl, ring-substituted by hydroxyalkyl and aminoalkyl, pyrimidinyl, pyrazinyl or quinoxalinyl,

(B) 0.1 to 5% by weight of an anionic fluorinated surfactant,

35 (C) 0.1 to 25% by weight of an ionogenic fluorine-free surfactant,

(D) 0.1 to 40% by weight of a non-ionic fluorine-free surfactant,

(E) 0 to 70 wt .-% of a non-aqueous solvent 4o and

(F) contain enough water to fill the rest up to 100%.

The present invention furthermore relates to the aqueous film-forming concentrates diluted with water and to these compositions, which contain a propellant and can be dispersed from a suitable container as an aerosol, and to a fire-fighting method (extinguishing and prevention) in which these compositions are used.

so The compounds represented by the above formulas I and II, where Q has the constitutions (la), (2a), (3a), (4a) or (5a), are in solution in the form of their internal salts and are therefore amphoteric Surfactants.

Compounds of the formula III are obtained by imidizing 55 of compounds of the constitutions I and II

X = -NH- by heating, either as such or in solution, to a temperature in the range of 50 to 150 ° C, or preferably to a temperature of about 100 ° C. The compounds used according to the invention, in which Q has the 6o constitutions (la), (2a), (3a), (4a) or (5a), are prepared from maleic or itaconic anhydrides, thiols containing perfluoroalkyl groups and a polyamine or amino alcohol . They are typically prepared in two stages: first, the reaction of maleic anhydride or 65 itaconic anhydride with an equimolar amount of either an alcohol containing at least one tertiary amino group, or of a primary or second containing at least one further primary, secondary or tertiary amino group

628 247

the dear amine to form an intermediate unsaturated half ester or half amide of the formulas:

COO0

HC

HC

©

'COX-QH

respectively.

H-, C = CH-COO0

CH2-COX-QH,

where X has the meaning given above and Q has the constitutions (la), (2a), (3a), (4a) or (5a).

Compounds of this formula are described in the literature as comonomers for vinyl polymerization, for example in US Pat. No. 2,821,521, where the N- (3-dimethylamino-propyl) maleic acid amide of the formula

CH-COO0

©

CH-CONH (CH2) 3N (CH3) 2H

is called.

For compounds in which X is -N-CH3 or -N-C2H5 and Q-CH2CH2-N (CH3) 2, the intermediate is cyclized to form a compound of the constitution:

H3C n © / CH3

/ N \ / CH2COO

0

I H I

V% 0

I.

CH3 (or -C ^).

These are new compounds and their constitutions have been confirmed by NMR and the absence of acidic hydrogen.

Instead of producing the intermediate from the anhydride by ring opening, other synthetic routes can be followed, such as transesterification or transamidation of a maleic, fumaric or itaconic acid lower alkyl half ester.

The synthesis of the new surfactants is completed in a second reaction stage, during which the perfluoroalkyl-substituted thiol is attached to the double bond, the intermediate, by base catalysis. This reaction normally proceeds at room temperature, unless an intermediate of the cyclic type described above forms; in this case, the thiol only accumulates at temperatures of 85 ° C and above.

On the other hand, one can reverse the synthetic route and attach the RrThiol to the unsaturated cyclic anhydride or its lower alkyl half-ester by base catalysis or a radical mechanism. The intermediate product is then reacted with an alcohol containing at least one tertiary amino group or with a primary or secondary amine containing at least one further primary, secondary or tertiary amino group, the desired product being obtained. Because of the high yield and purity of the product, the first synthetic route is preferred.

The monoesters can be easily synthesized by reacting the equimolar amount of an unsaturated cyclic anhydride and the amino alcohol, either neat or in solution. The monoamides can be

Prepare molar amounts of an unsaturated cyclic anhydride with a polyamine at a temperature below 50 ° C in a solvent. Solvents such as methyl ethyl ketone, diethylene glycol dimethyl ether, dimethyl sformamide, tetrahydrofuran, perchlorethylene, 1,1,1-trichloroethane, dichloromethane, dioxane, dimethyl sulfoxide and N-methylpyrrolidone are suitable. As described in more detail in Canadian Patent 828 195, the amides can also be prepared in water or a mixture of water and a solvent mentioned above by adding the anhydride to the aqueous solution of the amine.

The addition of the R-substituted thiol to the monoesters and monoamides is carried out in solution or undiluted at a temperature between 20 ° and 100 ° C. Possible solvents are alcohols such as methanol, ethanol, n-propanol, isopropanol, n- and isobutanol, amyl alcohol, n-hexanol, cyclohexane, benzyl alcohol, ethers such as dimethyl ether, methyl ethyl ether, diethyl ether, di-n-propyl ether, di -isopropyl ether, methyl-n-butyl ether, ethyl-n-butyl ether, 20 ethylene glycol dimethyl ether, divinyl ether, diallyi ether, tetrahydrofuran, ketones such as acetone, methyl ethyl ketone, methyl n-propyl ketone, diethyl ketone, hexanone-2, hexanone-3, methyl t-3 butyl ketone, di-n-propyl ketone, diisopropyl ketone, diisobutyl ketone, chloroacetone, diacetyl, acetylacetone, mesityl oxide, cyclo-25 hexanone; N-methylpyrrolidone, dimethylformamide, acetonitrile, benzene, chlorobenzene, chloroform, methylene chloride, carbon tetrachloride, dioxane, nitrobenzene and toluene. Water or a mixture of water and any of the foregoing solvents can also be used.

30 methanol, ethanol, isopropanol, diethylene glycol monomethyl ether or diethylene glycol methyl butyl ether and water-containing solvent mixtures are preferred. If it is necessary to remove the alcohol for a subsequent reaction, for example quaternization with propane sultone, a mixture of N-methylpyrrolidone and a low-boiling alcohol such as methanol is preferred. Since the maleic acid monoesters or maleic acid monoamides already contain an amino group, the addition of further amine as a catalyst for the thiol addition is not necessary.

40 The new surfactants thus obtained are readily soluble in water or water / auxiliary solvent mixtures, and the solutions are essentially neutral. In dilute aqueous solution, the tertiary aminoalkyl monoesters and monoamides form polymeric aggregates which have very high viscosities; these gel-like solutions can easily be broken up by adding an auxiliary solvent such as butyl carbitol or a non-ionic auxiliary surfactant such as an ethoxylated alkylphenol.

The compounds used according to the invention, in which Q 50 corresponds to the constitutions (1b and c), (2b and c), (3b and c), (4b and ç) and (5b and c), are prepared by quaternization; of the amphoteric surfactants described above.

The quaternization reaction can be carried out in the presence or absence of an inert solvent. Diethyl ether, acetonitrile, dimethylformamide, N-methylpyrrolidone, etc. are suitable as solvents.

The temperature for the reaction is not critical and, depending on the reactivity of the Quaternization-60, can range from 0 ° C. to about 150 ° C.

If an indifferent solvent is used, the quaternary ammonium compounds obtained are often obtained as solids. They can be easily separated, washed and dried. The products, as known to the person skilled in the art, can be isolated from a solution by adding a non-solvent. If desired, the products can be further purified by recrystallization from a suitable solvent or solvent mixture. As viscous liquids,

7

628 247

Products can be further cleaned by extraction with a suitable solvent.

If the amino alcohol is a diol or a polyamine containing at least three amino groups, at least two of which are primary or secondary, it can be reacted with two moles of maleic or itaconic anhydride and two moles of Rf-alkylenediol so that bis-Rf-alkylenediosuccinic acid halamides , -haibester and -succinimide arise, which are represented by the formulas rf-r'-s- (ch2) y-ch-cooh and their isomer or

rj-r1-s- (ch2) y-c-c I

h2c-c ch, cox-

H .0

N-

O

wherein T represents a divalent nitrogen-containing group selected from

(1)

2 / ^ - R ~ N

3rd

\

(R2) -

ho (ch2) 12-n (ch3) 2 ho-ch-ch2n (ch3) 2 I

ch3

5 H0- (CH2CH20) xCH2CH2-N- (CH2) zCH3 (CH2CH20) yh with x + y = 3-25 and z = 1-20 HO-CH2ch2-n (phenyl) CH2ch2OH HO-CH2ch2-n (tolyl) CH2CH2oh ho-ch-ch2-n (phenyl) CH2c H-OH io II

ch3 ch3

high 2ch2-n-ch2ch2ok c2h5, oc2h5

Cyclic compounds of the formula

20 (2) ho-r2-nqf in which R2 and Y have the meaning given above represent a further group of tert-arino alcohols.

Examples are illustrative of the above alcohols

25th

K H

15 CH, -P = 0

HO (CH2) 2

HO (CH2) 2 - Nv H

(2)

NO. 2-

v_ /

35 / \

H.O (CH) 2 N H O

(3)

-R "l

'

/ \

HOtCH) - N H N - (CH2) 3OH

where R9 represents the triradical of an aliphatic hydrocarbon having 3 to 10 carbon atoms, preferably 3 to 5 carbons. An example of formula (3) is 3-pyridylpropane-1,3-diradical.

When X in formulas I and II is oxygen, Q is derived from alcohols of the formula which contain tertiary amino groups

"R3

45

(l) HO-R2-N

\

R4

CH.

O

Still other classes of tertiary amino alcohols have the formulas

Z ei in which R3 and R4 have the meaning given above.

Examples to explain the alcohols listed above are ho-ch2 -ch2- (ch3) 2

HO-CH2-CH2-N (C2H5) 2

ho- (ch2) 3-n (ch3) 2

ho- (ch2) 3-n (c2h5) 2

ho - (ch2) 3-n (c3h7) 2

ho- (ch2) 4- (ch3) 2

ho- (ch2) 5-n (ch3) 2

ho- (ch2) 6-n (ch3) 2

ho (ch2) g-n (ch3) 2

ho (ch2) 10-n (ch3) 2

(3)

liO-R-l-

55

60

65

(4)

HO-R

(5) H0 (R) ^ - E

or or

628 247

8th

wherein R2, Z, E, a, b and k have the meaning given above.

Illustrative examples of such alcohols are

2-, 3- and 4- (2'-hydroxyethyl) pyridine,

3-methyl-4- (2'-hydroxyethyl) pyridine,

2-methyl-4- (2'-hydroxyethyl) pyridine,

2-, 3-, 4-, 5-, 6-, 7- and 8- (2'-hydroxyethyl) quinoline and

3-pyridyl-l, 5-pentanediol.

If X in the formulas I or II is -NR, such a group can be derived from a primary or secondary amine containing at least one further amino group. Such amines can be represented by the formula

Illustrative examples of the above amino are N- (2'-aminoethyl) piperidine, N- (2'-aminoethyl) morpholine, N- (4'-amino-nobutyl) piperidine, N- (2'-aminoethyl) pyrrolidine, N-methyl-pi-perazine, piperazine and N- (2-hydroxyethyl) piperazine.

5 Still further classes of primary and secondary amino containing at least one further amino group are aromatic heterocyclic compounds with five and six rings, including

R

(1) hn- (r2) k-n '

, R3 -R4

wherein R to R4 and k have the meaning given above, are shown.

Examples to explain the amines listed above are nh2 (ch2) 2n (ch3) 2 nh2 (ch2) 2n (c4h9) 2 œ3nh (ch2) 2n (ch3) 2 nh2 (ch2) 3n (c3h7) 2 nh2 (ch2) 4n ( qhs),

nh2 (ch2) 5n (c2h3) 2 nh2 (ch2) 8n (c3h7) 2 nh2 (ch2) 2n (c2hs) 2 nh2 (ch2) 3n (ch3) 2 ch3nh (ch2) 2n (c2h3) 2 nh2 (ch2) 3n (c3h7) 2 ch3nh (ch 2) 4n (ch3) 2 NH.CCH ^ NCQHs),

nh2 (ch2) 8n (c4h9) 2 nh2 (ch2) 2n (c3h7) 2 nh2 (ch2) 3n (c2h5) 2 c2h5nh (ch2) 2n (c2h5) 2 nh2 (ch2) 4n (ch3) 2 nh2 (ch2) sn (ch3) 2 nh2 (ch2) 6n (c3h7) 2 nh2 (ch2) 10n (c3h7) 2 nh2 (ch2) 12n (c3h7) 2 ch3nh (ch2) 3n (ch 3) 2 h2n (ch2) 2n (ch2ch2oh) 2 h2n-n (ch3) 2 ch3nh-n (ch3) 2

h2nchxh2ch2nhch3

h2nch2ch2nhch3

h2nch2ch2ch2nh2

h2nch2ch2nh2

h2nch2ch2nhch2ch2oh.

A further class of primary and secondary amines containing at least one further amino group are heterocyclic compounds of the formulas and

(5)

H2N (R2) k-E

30th

35

40

50

wherein R, R2, Z, E, a and b have the meaning given above and v is zero or an integer from 2 to 12. Illustrative examples of the amines listed above are

2- (2'-aminoethyl) pyridine, 3- (2'-aminoethyl) pyridine, 2-methyl-3- (2'-aminoethyl) pyridine, 3- (4'-aminobutyl) pyridine, 4- (2nd 'Aminoethyl) pyridine, 2-aminopyridine, 3-, 4-, 5- or 6-methyl-2-aminopyridines, 3-, 4-, 5- or 6-chloro-2-aminopyridines,

3-aminopyridine, 2-chloro-6-methyl-3-aminopyridine, 4-aminopyridine, dichloro-4-aminopyridine, 2-aminopyrimidine, 2-, 3-,

4-, 5-, 6-, 7- and 8- (4'-aminobutyl) quinolines, 2-, 3-, 4-, 5-, 6-,

7- and 8- (3'-Methylaminopropyl) quinolines, 2,3,4,5,6,7 or

8-aminoquinolines, chloraminoquinolines, methylaminoquinolines, guanine and adenine.

Compounds of the formulas I, II or III, in which Q has the constitution (Ib), (2b), (3b), (4b) or (5b), are from the corresponding amines by quaternization with compounds of the constitution

R5A,

wherein R5 and A have the meaning given above, derived.

(2)

HN- (R) -N Y or

R

/ V p

HN H N-R-

\

y wherein R, R2, R5 and Y have the meaning given above.

Suitable compounds of the formula R5 A are those in which R5 represents an alkyl group having 1 to 18 carbon atoms and A is any anion which forms an ammonium salt of the formula NH4®A0 with a water solubility of 55 at least 1%. Examples of R5A include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, hexyl, octyl, ethylhexyl, decyl, dodecyl, tetradecyl, hexa- decyl and octadecyl chlorides, bromides and iodides, benzyl chloride, haloalkanoic acid esters and haloalkyl alkyl ethers 60 are considered.

Normal alkyl halides, i.e. n-Propyl, n-butyl, n-octyl or n-hexadecyl are preferred. The toluene, benzene and chlorobenzenesulfonate esters of methyl, 65 ethyl, propyl, butyl and similar alcohols, and methyl and ethyl sulfate are also suitable. When using methyl or ethyl sulfate (R2S04) is usually a mixture of RS04 and

9

628 247

SO.

t0 JRR

S (CH2) yCHCOOH CH2COX-Q

present as anion A in the product according to the invention. Mineral acids such as HCL, HBr, HJ, H3P04 and H2S04 as well as organic acids such as acetic, formic and acrylic acid can also be used.

Compounds of the formulas I, II and III in which Q has the constitution (1c), (2c), (3c), (4c) or (5c) are similarly derived by quaternization

(a) Hal-R6-COOH

wherein shark is chlorine, bromine or iodine and R6 is an alkylene group with 1 to 5 carbon atoms or a group

-CH- -C-

I II

CH2COOH represents CH-COOH,

(b) r10-chch2 co or β-lactones

(c) ch2ch2-so2

substituted ethylene (Rr-CH = CH2) obtained by dehydrohalogenation of the halide Rf-CH2CH2-Hal.

The reaction of the iodide Rf-R1-J with thiourea with 5 subsequent hydrolysis to the mercaptan Rf-R'-SH represents the preferred route of synthesis. The reaction is applicable to both linear and branched-chain iodides. Numerous valuable perfluoroalkoxyalkyl iodides of the general formula

10th

20th

25th

(cf3) 2cfo cf2cf2 (ch2ch2) mj where m is 1-3 are described in U.S. Patent 3,514,487.

Thiols of the formula rfch2ch2sh in which rf is perfluoroalkyl having 6 to 12 carbon atoms are particularly preferred. The following rf-thiols can be produced from rjch2ch2j and thiourea in very high yield.

C4F9CH2CH2SH

C6F13CH2CH2SH

csF17ch2CH2sh c10f21ch2ch2sh c12f25ch2ch2sh chr o

CF3 ^

30cf3 /

CFO (CF2CF2) 1 to 3 CH2CH2SH

Propane sultone in which R10 is hydrogen or an alkyl group having 1 to 6 carbon atoms, from the corresponding amines.

The perfluoroalkylthiols used in the preparation of the compounds used according to the invention are well known to those skilled in the art. For example, thiols of the formula RjR1 -SH are available in a number of U.S. Patents including 2,894,991,

2 961 470.2 965 677.3 088 849.3 172 190.3 544 663 and

3,655,732.

So U.S. discloses U.S. 3,655,732 mercaptans of the formula rf-r'-sh wherein R1 is alkylene of 1 to 16 carbon atoms and R {is perfluoroalkyl, and teaches that holgenides of the formula Rp-R'-hal are well known; Reaction of RfJ with ethylene under radical conditions gives R {(CH2CH2) aJ, while reaction of RfCH2J with ethylene gives RfCH2 (CH2CH2) aJ, as further described in U.S. Patents 3,088,849,3,145,222, 2,965,659 and 2,972,638.

U.S. Patent 3,655,732 further discloses compounds of the formula rf-r'-x-r "—sh wherein R 'and R" are alkylene of 1 to 16 carbon atoms, the sum of the carbon atoms in R' and R "not exceeding 25; Rf is perfluoroalkyl of 4 to 14 carbon atoms and x is -S- or -NR "', where R"' is hydrogen or alkyl of 1 to 4 carbon atoms.

The U.S. Patent 3,544,663 teaches that mercaptan is used

RfCH2CH2SH

where Rf is perfluoroalkyl having 5 to 13 carbon atoms, by reacting the perfluoroalkylalkylene iodide with thiourea or by adding H2S to a perfluoroalkylsub-

As perfluoroalkylalkylene thiols are C6F13CH2CH2SH C8F17CH2CH2SH 35 C10F21CH2CH2SH

and their mixtures are particularly preferred.

Suitable unsaturated, cyclic dicarboxylic anhydrides which can be used in the preparation of the surfactants according to the invention are maleic anhydride and alkyl- and halo-40-substituted maleic anhydrides such as citraconic anhydride and chlorine and dichloromaleic anhydrides. Ita-con and maleic anhydride are preferred, and especially maleic anhydride.

The surfactants used according to the invention can in particular be used as wetting agents in coatings, waxes, emulsions and paints. As a preparation with other non-fluorinated surfactants, they are particularly valuable fire-fighting agents. A particular advantage of these surfactants is their low toxicity for 50 organisms living in water.

A particular advantage of the compounds used according to the invention, in which Q has the constitution (Ia), (2a), (3a), (4a) and (5a), is that without the step of using carcinogenic alkylating agents such as 55β -Lactones and propane sultones requiring special quaternization reaction are manufactured amphoteric surfactants. Such a quaternization step is necessary in the case of known amphoteric surfactants. The compounds of the formulas (I), (II) and (III) are particularly valuable in the preparation of 60 aqueous fire-fighting preparations, especially when used in combination with non-fluorinated surfactants. Such preparations have superior properties in hydrocarbon firefighting.

Preferred surfactants are the amphoteric surfactants of For-65 mein Ia and IIa, in which Q has the constitution (la), (2a) or (3a). Particularly preferred are those in which R 1 is linear perfluoroalkyl having 6 to 12 carbon atoms, R1 is ethylene and y is zero. Very particularly preferred surfactants are those

628 247 10

where X stands for NR and Q corresponds to the constitution (la), and especially where costly facilities have to be protected,

where R2 for straight-chain alkylene with 2 to 5 carbon atoms can be used in a variety of ways, generally

men stands and R hydrogen, methyl or ethyl and R3 and R4 mine using the usual portable foam nozzles

Mean methyl or ethyl. on hand-held hoses, but also according to other

It is also well known that methods such as with vibrating tower foam nozzles, immersion spray devices of various types of RF surfactants, such as, for example, non- (petroleum tank storage), stationary, non-suctioning sprinkler systems are used.

ionic and anionic surfactants, for themselves or together (chemical operating zones, refineries), underfloor

with conventional hydrocarbon auxiliary surfactants, such as through and hangar ceiling flooding systems,

Bernett and Zisman (J. Phys. Chem. 65, 448, (1961)) reports, built dosing systems (induction dosing devices), or aerosol

synergistic surface tension effects achieved. 10-type dispensing devices, such as those used in the home or in vehicles.

Furthermore, Tuve et al. in U.S. 3 258 423 would apply the gene. AFFF funds are used as fire

use of aqueous solutions of certain Rt surfactants or Rr agents for Class A fires such as wood, textile, paper,

Surfactant mixtures for themselves or together with solvents, rubber or plastic fire or class B fires and other additives as effective fire-fighting agents. flammable solvent, petrol, gas or grease fires, especially

Based on the findings of Tuve et al. 15 of them are the latter, recommended. When used correctly, additional fire extinguishing agents containing various Rf surfactant systems or together with chemical dry extinguishing agents (double

ordnance became known as in U.S. 3 315 326 and systems) they also produce a vapor-covering foam

3772 195. amazing protective effect.

Fire-fighting agents containing RrTenside generally work in two directions: AFFF agents have set and exceeded 20 fuel taxes.

a. In the form of foams, they are used as primary fen by far the performance of any previously used fire fighting means. Protein foams. However, the performance of today's hand

b. As agents that suppress the evaporation, commercially available AFFF agents are not yet the last demands made by the inducer of a re-ignition of fuels and solvents. The very high price of AFFF funds. 25 means restricting widespread use and it is therefore abso-

It is precisely this second property that gives the fluorochemical fire-fighting agents, more effective AFFF agents, which, in order to achieve the fire-fighting agents, require their great superiority over all the same effects of fewer fluorochemicals, than other known fire-fighting agents. wrap. Furthermore, the secondary properties are unavoidable

Such fire retardants are generally to be improved as the currently available AFFF agents. The

AFFF (i.e. aqueous film forming foams) should:

end foams]). The effect of the AFFF agent a) a lower degree of toxicity (poisoning of fish is caused by the fact that the RrTenside the surface is a very essential point wherever AFFF agent in

Reduce the tension of aqueous solutions to such an extent that the solutions are released in large quantities and where it is possible to wet and spread solutions of non-polar and water-immiscible solvents for the contamination of receiving waters (rivers and lakes), even though such solutions exist ; this is an important problem in test benches

are moderately lighter than water; they are a barrier to fires, where AFFF funds are often used);

substance or solvent vapor, which means the flames quickly b) lower chemical oxygen demand (COD); good extinguished and reignition and re-ignition prevents biodegradability (to the activity of microorganism

will. Not to hinder the achievement of a spontaneous spread of two men in biological cleaning systems);

Harkins 40 c) criterion necessary for immiscible phases is less corrosive properties, so that they can be easily

et al., J. Am. Chem. 44.2 665 (1922). They are made of aluminum and not heavy, corrosion-free

Measurements for the tendency to spontaneous spreading can be used as follows;

defined by the spreading coefficient (SK): d) improved long-term storage stability;

,. , e) good compatibility properties with conventional chemical

where SK = Ya-Yb-Yg 45 see dry chemical;

Prei nfs oe ment f) improved sealing of vapors and sealing

YU = surface tension of the lower liquid phase speed; and the most important:

Yb = surface tension of the upper aqueous phase g) s0 have a high performance that they apply Yg = interfacial tension between the aqueous or the AFFF agent in 1% dosing systems or below and the lower liquid phase. 50 anstejje the use of 3 and 6% dosing systems

If the SK is positive, the surfactant solution should spread and become possible. This means that 1 part of an AFFF member

Filming occur. The higher the SK, the greater the amount is mixed or diluted with 99 parts of water

Spreading tendency. This requires the smallest possible watery can. The importance of such high-performance

Surface tension and the lowest interfacial tension is that the storage requirements for the AFFF averaging, as would be greatly reduced with mixtures of one or more 55 or, in the case where storage installations are made up of certain surfactants and common hydrocarbon surfactants, the capacity for available firefighting

sid mixes achieved. tel would be greatly increased. AFFF agent for 1% dosing systems

Commercial AFFF agents are nowadays heard - are therefore of great importance wherever the stocks are used in so-called 6% and 3% dosing systems. Capacity is limited as on offshore oil wells, 6% means that 6 parts of an AFFF agent and 94 parts of 60 offshore nuclear power plants, or municipal fire fighting water (fresh water, sea water, or brackish water) are mixed. The amount or quantity expected today from an AFFF agent and at the respective place of use by means of conventional equipment has been officially established in most countries (for example, uses foam generators. Similarly, US Navy Military Specification MIL-F-24 385 with late An AFFF agent for a 3% dosage of such supplements is mixed).

that 3 parts of this agent and 97 parts of water are mixed and 65 The novel novel AFFF described

be applied. Compared to today's AFFF funds, funds are not

At present, AFFF funds are used wherever there is a need for time to bring the fire under control only with regard to the primary performance characteristics, such as the risk of fuel or solvent fires

11 628 2AT

Extinguishing time and the re-ignition resistance, superior, alkylene, sulfonamidoalkylene or carbonamidoalkylene residues, but in addition they allow because of their very high existing, multivalent link and Z for a from anio-

Effectiveness also an application in 1% dosing systems. African residues, water-solubilizing, polar

Furthermore, from the standpoint of ecology and host group, they offer corresponding water-soluble fluoroaliphatic economy, desirable secondary properties. 5 represents connection.

To form effective compositions, a Ge -C02 ~ and -S03 ~ are preferred as anionic groups,

mix of the various surfactants surface tension of To achieve suitable solubility properties, this should reach less than about 26 dynes / cm. Each component (A) anionic surfactant can contain 30-65% carbon-bonded fluorine to (E) from a certain compound or from one. The anionic surfactant can be a free acid or

Mixture of compounds exist. 10 whose salt with an alkali metal, ammonium or substitute

The above composition represents a concentrate which contains ammonium.

ches, as indicated above, when diluted with water by the acids listed below and their alkali metal salts

Formation of a foam which is a tough film on the surface are illustrative examples of the

deposits of the flammable liquid, the other concentrates of which can be used Rf anion-active surfactants. Prevents vaporization and thus extinguishes the fire, a highly effective patent number given in 15 brackets refer to Pa-

me formulation for fire fighting. in which the respective class of compounds

It represents a preferred fire extinguishing agent for fire of which details are disclosed.

flammable solvents, especially for hydrocarbons and polar solvents with low water solubility, for carboxylic acids and their salts, for example for 2oRfCOOH (Scholberg et al. J. Phys.

Hydrocarbon fuels - such as gasoline, heptane, toluene, Chem. 57,923-5 (1953)

Hexane, aviation fuel, VMP naphtha, cyclohexane, Ter-Rf (CH2) i_2oCOOH (DT 1 916 669)

pentin and benzene; RfO (CF2) 2.20COOH (DT 2132164)

polar solvents with low water solubility - such as Butylace- RfO (CF2) 2_2o (CH2) 2_2oCOOH (DT 2 132 164)

tat, methyl isobutyl ketone, butanol, and ethyl acetate, and 25 RfO (CH2) ^ oCOOOH (US 3,409,647)

polar solvents of high water solubility - such as methanol, RfS02N (C2H5) CH2C00H (US 3 258 423)

Acetone, isopropanol, methyl ethyl ketone, ethyl cellosolve and so Rf0 (CF20) 3CF2C00H (F 1 531 902)

continue. RfO / CF2CFO \ CF2COOH (F 1 537 922)

d / cf2cfo \ <

(ij

They can be used simultaneously or in succession together with flame-suppressing chemical dry powders such as Na-30

trium or potassium bicarbonate, ammonium dihydrogenphos RfO [CF (CF3) CF2] CF (CF3) CON (CH3) CH2COOH

sphat, C02 gas under pressure or Purple K, or also in söge (US 3 798 265)

called double agent systems apply. The ratio che- (C2F5) 2 (CF3) CCH2COOH (GB 1 176 493)

Mix dry powder to AFFF agent could be 4.5 to 13.6 kg CI0F19OC6H4CON (ch3) CH2COOH (GB 1 270 662) dry chemical powder to 7.5 to 37.853 1 AFFF agent in 35 Rf (CH2) 1_3SCH (COOH) CH2COOH ( US 3 706 787)

the application concentration is (i.e. after dosing Rf (CH2) 1_12S (CH2) 1_17COOH (DE 2 239 709;

to 0.5%, 1%, 3%, 6% or 12%). As a typical example US3 172900)

you could use 9 kg of dry chemical powder and 18.9 1

Use AFFF funds. The composition sulfonic acids and their salts according to the invention can also be used together with hydrolyzed protein "RfS03H (US 3,475,333)

or use fluoroprotein foams. RfCäH4S03H (DE 2 134 973)

The foams of the present invention neither fall to Rf (CH2) ^ gSO ^ H (DE 2 309 365)

together, they still have other adverse reactions R £ S02NHCH2C6H4S03H (DE 2 315 326)

with a dry powder such as Purple-K powder (P-K-P). RfS02N (CH3) (C2H4O) 1_20SO3H (South Afr. 693 583)

Purple-K powder is the common name for a potassium bi- 45 RfCH2CH30CH2CH2CH2S03H (Kan. 842 252)

carbonate fire extinguishing agent, which is flowable and easy Rf0C6H4S03H (DE 2 230 366)

as a powder cloud over flammable liquid and other fire Ci2F230C6H4S03H (DE 2 240 263)

he sprinkles. (C2F5) 3C0 (CH2) 3S03H (GB 1 153 854)

Usually the concentrate is diluted with water CF3 (C2F5) 2C0 (CH2) 3S03H (GB 1 153 854)

using a dosing system such as a 50 (C2F5) 2 (CF3) CCH = C (CF3) S03H (GB 1 206 596)

3% or 6% dosing system in which 3 parts or 6 parts of RfOCF (CF3) CF2OCF (CF3) - (US Pat. No. 3,798,265) concentrate are mixed with 97 or 94 parts of water. C0NHCH2S03H This highly diluted aqueous composition is then used to extinguish and control the fire. Phosphonates, phosphates and related phosphorus derivatives as well

Component (B) is a fluorinated, anionic ten- their salts. The constitution of these surfactants in detail is not critical. RfPO (OH) 2 (Rf) 2PO (OH) (DE 2 110 767)

table. You can e.g. by the formula RfS02N (Et) C2H40P0 (0H) 2 (DE 2 125 836)

RfCH2OPO (OH) 2 (DE 2 158 661)

RfQmZ C8F15OC6H4CH2PO (OH) 2 (DE 2 215 387)

«0 RfOC6H4CH2PO (OH) 2 (DE 2 230 366)

describe in which Rf is a fluorinated, saturated monovalent non-aromatic radical having 3 to 20 carbon atoms, the rest (and their salts);

in which the chain carbon atoms only by fluorine, chlorine or RfS02N (CH3) C2H40S03H (DE 1 621 107)

Hydrogen atoms with no more than one hydrogen or RfC6H4OH (US 3,475,333)

Chlorine atom are substituted on two carbon atoms and in 65 Rf (CH2)! _ 20S2O3Na (DE2 115 139)

which may have a divalent Rf (CH2) 1_20SO2N (CH3) - (DE 2 115 139) oxygen atom or trivalent nitrogen atom only bonded to carbon atoms in the framework chain CH2CH2S203Na, Qm, where m is the number 0 or 1, for one of RfS02H (US 3 562 156)

628 247

12

The reaction of 1,3-propanesuIton with a per-fluoroalkylthiol of the formula rr-r, -s- (ch2) 3s03gz®

where R and Z have the meaning given above and R1 the meaning given below, the type of compound formed is particularly preferred as the fluorinated anionic surfactant of the sulfonate class.

The perfluoro-alkylthiols used in the manufacture of the sultons are well known in the art. For example, thiols of the formula RfR'-SH are used in numerous U.S. Patents, including 2,894,991.2,961,470.2,965,677, 3,088,849.3,172,190, 3,544,663 and 3,655,732.

So the U.S. discloses Patent 3,655,732 mercaptans of the formula

Rr-R ^ H,

where R1 is alkylene of 1 to 16 carbon atoms and Rf is perfluoroalkyl, and teaches that halides of the formula R (—R'-hal are well known; reaction of RfJ with ethylene under radical conditions gives R £ (CH2CH2) aJ,

during reaction of R £ CH2J with ethylene leads to R £ CH2 (CH2CH2) aJ, as further described in U.S. Patents 3,088,849.3,145,222.2,965,659 and 2,972,638.

The U.S. Patent 3,655,732 further describes compounds of the formula rj-r1-x-r 'sh wherein R1 and R "for alkylene of 1 to 16 carbon atoms, the sum of the carbon atoms in R1 and R" not exceeding 25, Rf for perfluoroalkyl 4 to 14 carbon atoms and X is -S— or —NR "with R" 'being hydrogen or alkyl with 1 to 4 carbon atoms.

The preferred synthetic route for the formation of the mercapane rf-R'-SH is the reaction of the iodide rf-R'-J with thiourea with subsequent hydrolysis. The reaction is applicable to both linear and branched chain iodides. Numerous valuable perfluoroalkoxyalkyl iodides of the general formula

(CF3) 2CFO CF2CF2 (CH2CH2) mJ

where m is 1-3 are described in U.S. Patent 3,514,487.

Below are the thiols of the formula

RfCH2CH2SH,

where Rt is perfluoroalkyl having 6 to 12 carbon atoms, particularly preferred. These RpThiole can be produced in a very high yield from RfHC2CH2J and thiourea.

Component (C) as an ionogenic, fluorine-free, water-soluble surfactant is selected from aion-active, cation-active or amphoteric surfactants, as described in Rosen et al., Systematic Analysis of Surface-Active Agents, Wiley-Interscience, New York (2nd edition , 1972), pages 485-544.

It is particularly expedient to use amphoteric or aion-active fluorine-free surfactants, since these are relatively insensitive to the effects of the fluoroaliphatic surfactant structure or to the ion concentration in the aqueous solution and are also available in a wide range of relative solubilities, which facilitates the selection of suitable materials.

The main consideration in the selection of preferred ionogenically fluorine-free surfactants is that they have an interfacial tension below 5 dynes / cm at concentrations of 0.01-0.3% by weight. They should continue to have high levels of foaming at their application concentrations, heat-stable, acid and alkali-resistant, biodegradable at practical application and storage temperatures, especially non-toxic to organisms living in water, easily dispersible in water, insensitive to hard or sea water and with be compatible with anion-active or cation-active systems, form protective coatings on materials, be pH-insensitive, commercially available and inexpensive.

According to the classification scheme found in Schwartz et al., Surface Active Agents, Wiley-Interscience, NY, 1963, anion-active and cation-active surfactants become firstly according to the type of their solubilizing or hydrophilic group and secondly according to the mode of binding of the hydrophilic and hydrophobic Groups, ie described directly or indirectly, and if indirectly according to the type of binding.

The description of amphoteric surfactants as a pronounced chemical category is based on the fact that they contain both anionic and cationic groups and, depending on their isoelectric pH range and the degree of charge separation, have special behavior.

Typical anionic surfactants include carboxylic acids, sulfuric acid esters, alkane sulfonic acids, alkyl aromatic sulfonic acid and compounds with other anionic hydrophilic functions, e.g. phosphates and phosphonic acids, thiosulfates, sulfinic acids, etc.

Because of their hydrolytic stability and easy accessibility, carboxylic or sulfonic acids are preferred. The following may be mentioned as illustrative examples of anion-active surfactants: C11H230 (C2H40) 3 5S03Na C “H230CH2CH20S03Na C12H250S03Na

Alkyl diphenyl ether disulfonate disodium salt

Sulfo- derived from an ethoxylated C10.12 alcohol

succinic acid disodium salt

Sodium alpha olefin sulfonates

CnH23C0N (CH3) C2H4S03Na

CnH23C0N (CH3) CH2C02Na

Typical cation-active classes include amine salts, quaternary ammonium compounds and other nitrogen-containing and nitrogen-free bases, e.g. Phosphonium, sulfonium and sulfoxonium; also the special case of amine oxides, which can be regarded as cation-active under acidic conditions.

For reasons of stability and easy accessibility, amine salts, quaternary ammonium compounds and other nitrogen bases are preferred. In terms of corrosion, cation-active compounds containing no halide are preferred. The following are examples of cationic surfactants:

Bis (2-hydroxyethyl) tallow amine oxide hydrogenated dimethyl tallow amine oxide isostearylimidazolinium ethosulfate cocosylimidazolinium ethosulfate lauroylimidazolinium ethosulfate

[C12H25OCH2CH (CH) CH2N (CH3) CH2CH2OH) 2]

ch3so4®

[Q! H23CONH (CH2) 3N (CH3) 3] CH3S04q [C17H35CONH (CH2) 3N (CH3) 2CH2CH2OH] NO3®

Amphoteric fluorine-free surfactants include compounds which contain the following groups in the same molecule: amino and carboxyl, amino and sulfuric acid ester, amino and alkanesulfonic acid, amino and aromatic sulfonic acid.

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

13

628 247

such as various combinations of basic and acidic groups, as well as the special case of amine imides.

Those fluorine-free amphoteric compounds which contain amino and carboxyl or sulfo groups and the amine imides are preferred.

Aminimide surfactants are described in Chemical Reviews Volume 73, No. 3 (1973), which is hereby expressly pointed out. Generally, these are carboxamine imides of the general formulas:

O

N

CH.

5C H 11 23

4- (

SS

-CH2CH2OCH C02

CH .CO, Na

1 2

II R

11 - + /,

R (H) n-C-N-N-R2 \ 3

o or

R1 R R (H) "- C-N-N-CHR4 -C-OH and sr * st6

Sulfonylamine imides of the general formulas:

R1

- + /

J-

/

R (H) nS02N-N-R2 or R (H) nS02N-NCHR4-C OH

Sr3

x

R2

\

aminocyanimides, aminonitroimides or functionally substituted aminimides, as described in U.S. Pat. 3,499,032, U.S. 3 485 806 and GB 1 181 218.

Among the amine imides mentioned above, carboxamine imido is particularly preferred because of the combination of the extremely desirable surface-active properties listed below:

a) they are highly surface-active and have very low interfacial tensions in low concentrations and therefore provide films with an extraordinarily high spreading coefficient;

b) they are amphoteric and therefore compatible with any kind of fluoride sid - anion-active, cation-active, non-ionic or amphoteric;

c) they are heat-stable at practical application and storage temperatures;

d) they are acid and alkali resistant;

e) they are biodegradable and non-toxic;

f) they are easily dispersible in water;

g) they are highly foaming with only moderate sensitivity to water hardness;

h) they are cheap and commercially available.

The following are illustrative examples of non-fluorochemical amphoteric surfactants:

Coconut fat betaine (C02)

Cocosylamidoethylhydroxyethylcarboxymethylglycine betaine cocosylamidoammonium sulfonic acid betaine cetyl betaine (C-type)

A sulfonic acid betaine derivative

0 ©

C,, H23CONN (CH3) 2CHOHCH3

0 ©

c, 3H27conn (ch3) 2ch2chohch3 c15h31conn (CH3) 2 ch2chohch3

ci7H35conn (ch3) 2 ch2chohch3

c i, h23conn (ch3) 3

c13h27conn (ch3) 3

c15H3, conn (ch3) 3

A coconut derivative of the above coconut betaine

10 c12_14h25_29nh2ch2ch2coo-

(Triethanolammonium salt)

+ / CH2CH2C02-

15C12H25N '

I xCH2CH2C02Na H

The non-ionic fluorine-free surfactant component (D) is mainly added to the aqueous fire-fighting concentrates as a stabilizer and solubilizer for the compositions, especially when diluted with hard sea water. The non-ionic compounds are chosen mainly on the basis of their hydrolytic and chemical stability, R6 25 solvent-imparting and emulsifying properties (e.g.

according to HLB values, hydrophilic / lipophilic balance). Cloud point at high salt concentrations, toxicity and behavior during biodegradation. In the second place, the selection is made with regard to the degree of foaming, the viscosity of the foam, the foam drainage, surface tension, interfacial tension and wetting properties.

Typical classes of non-ionic surfactants which can be used according to the invention include polyoxyethylene derivatives of alkylphenols, linear or branched alcohols, fatty acids, mercaptans, alkylamines, alkylamides, acetylene glycols, phosphorus compounds, glucosides and fats and oils. Further non-ionogenic compounds are amine oxides, phosphine oxides and non-ionic compounds derived from block polymers containing polyoxyethylene and / or polyoxypropylene units.

Polyoxyethylene derivatives of alkylphenols, linear or branched alcohols and glucosides as well as block polymers of polyoxyethylene and polyoxypropylene are preferred, the first two being particularly preferred. 45 The following are illustrative examples of non-ionogenic non-fluorochemical surfactants:

Octylphenol (EO) 9> 10 octylphenol (EO) 16 octylphenol (EO) 30 so nonylphenol (EO) 9j10 nonylphenol (EO) 12] 3 lauryl ether (EO) 23 stearyl ether (EO) 10 sorbitan monolaurate (EO) 20 55 dodecyl mercaptan (EO) 10 block copolymer of (EO) x (PO) 4 CuH23CON (C2H4OH) 2 C12H25N (CH3) 20

60

c12h25n

(CH2CH20) XH (CH2CH20) yH

x + y = 25

65 Note: EO or PO as used above mean recurring ethylene or propylene oxide units.

Component (E) is a solvent that acts as an anti-freeze or foam stabilizer or for

628 247 14

Jung serves the refractive index so that the dosing systems under The present concentrate can also be easily from one

Practical conditions can be calibrated. This is not an effective aerosol container using a conventional inert loan-indispensable component of the propellant according to the invention such as Freon 11, 12 or 22 or N20, N2 or air composition, since highly effective AFFF concentrates are dispersed in. Expansion volumes up to a height of 50, absence of solvent can be obtained. Rather, 5 is achievable based on the air / liquid ratio.

This is one of the unexpected and unusual features that- The amphoteric surfactants of component (A) are this invention because prior art compositions are key elements in this novel AFFF system.

usually the use of a relatively high percentage- These amphoteric surfactants reduce the surface content of solvent. However, even with the tensions of the aqueous solutions to approximately 20 dynes / cm and compositions according to the invention, it is often advantageous to use a 10 as a solubilizer for the RrTenside of type (B), especially when the AFFF-Kon to which majority the excellent properties of the concentrate should be stored at frost temperatures. Contribute useful novel AFFF agents according to the invention. The funds are in U.S. Patents 3,457,172,3,422,011 and ionic surfactants of component (B) act as surfaces. 3,579,466 and German Patent 2,137,711. voltage reducer for the amphoteric surfactant

Typical solvents are alcohols and ethers such as 15 component (A) (synergistic RrTensidmischungen), which the

Ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, reduce surface tension to Ì5-16 dynes / cm and ge-propylene glycol monoalkyl ether, dipropylene glycol mono- habitually present in much lower concentrations than the Rr surfactants alkyl ether, triethylene glycol monoalkyl ether, 1-butoxyethoxy- der-. Furthermore, the RrTen-2-propanol, glycerin, diethyl carbitol, hexylene glycol, butanol, side of component (B) increase the spreading rate of t-butanol, isobutanol, ethylene glycol and other low-molecular-weight AFFF films on hydrocarbon fuels and specific alcohols such as ethanol or Isopropanol, in which they make an important contribution to the excellent

Contain alkyl groups 1-6 carbon atoms. sealability of the new AFFF agent. The ionogenic l-butoxyethoxy-2-propanol, diethylene glycol monobutyl or amphoteric hydrocarbon surfactants of the ether component or hexylene glycol are preferred as solvents. (C) perform a double function. They act as interfaces

Still other tension reducers, if any, are present in the formulation, in that they are the interfacial tension of the components: those containing components (A) and (B) as surfactants

- Buffers of a largely unrestricted type, for example aqueous RrTensidlösung of interfacial tensions by weise Sörensens phosphate or Mcllvaines citrate buffer. up to 10 dynes / cm to interfacial tensions as low as

- Unrestricted corrosion inhibitors as long as they reduce 0.1 dynes / cm. Furthermore, the auxiliary surfactants which are compatible with the other constituents of the formulation act as foaming agents, and by changing the properties of the formulation. Amount and proportions of auxiliary surfactants of component (C) can

- Chelating agents of an unrestricted type, for example polymerizing the degree of foaming of the novel AFFF agent va-lyaminopolycarboxylic acids, ethylenediaminetetraacetic acid. The non-ionic hydrocarbon surfactants of tronic acid, gluconic acid, tartaric acid, nitrilotriacetic acid and component (D) in the novel AFFF agent also practice hydroxyethyl ethylenediamine triacetic acid and its salts. 35 multiple functions by acting as a solution broker for

- High molecular foam stabilizers such as polyethylene - the surfactants of components (A) and (B) with poor glycol, hydroxypropyl cellulose or polyvinyl pyrrolidone. Solubility properties work. They also have stabilization

The concentrates according to the invention are fire-fighting agents with any pH effects, especially effective for AFFF agents / seawater-Vormi value, however, such concentrates with dilute acid or Al-40 agents and, in general, are influenced and influence the foam stability of the AFFF. as explained further below, the foam dewatering potash to a pH of 6 to 9, and particularly preferably for a period of time. They also have an influence on the viscosity of a pH of 7 to 8.5. Organic acids of the AFFF agent, which is particularly critical in the case of 1% dosage or mineral acids, such as acetic acid, oxalic acid, sulfuric acid, can be extremely critical. The solvents of the component or phosphoric acid, or metal hydroxides or amines, such as (E), are used in a similar way as solubilizers for sodium or potassium hydroxide, triethanolamine or tetrame 45 surfactants, but they also act as foam stabilizer ethyl ammonium hydroxide. ren are used to modify the refractive index for calibration

As mentioned above, the condensers according to the invention are dosed under practical conditions, reduce the viscous concentrates before use as fire-fighting agents with a high concentration of AFFF agents and act as diluted water. Although due to the availability of fire extinguishing agents. Whereas commercially available AFFF agents for 60% devices, which automatically contain the concentrate with water in such a dosage and have high solvent contents of over 20%, can mix ratios, the present invention teaches the preparation of comparable preparations and therefore the most practical ones preferred concentrations of said mines with excellent performance in solvent composition in water are 3% and 6%, there is no sustain that can go down to 3%.

Reason why the concentrate could not be used in lower concentrations of 0.5% to 3% or in higher concentrations. 55 Some of the 6% to 12% present in the AFFF preparations. This is only a solvent only because it is brought into the product from the question of expediency, the type of fire and the surfactant synthesis. Ne-

Extinguishing the flames desired effectiveness. There is still no contribution to be made by the components mentioned so far to the behavior of the new AFFF agent

An AFFF concen- tration very useful for a 6% dosing system to mention that these candidates were selected because of their very low level of toxicity, as shown in the examples.

A) 1.0 to 3.5% by weight of amphoteric fluorinated surfactant. As already mentioned, further additions to the

B) 0.1 to 2.5% by weight of anion-active fluorinated surfactant, novel AFFF agents may be advantageous, such as:

C) 0.1 to 4.0 wt .-% ionogenic fluorine-free surfactant, corrosion inhibitors (for example in the event that aqueous

D) 0.1 to 8.0% by weight of nonionic fluorine-free surfactant 65 AFFF premixes are stored for several years in uncoated aluminum and minium cans).

E) 0 to 20 wt .-% solvent and enough water, chelating agents (if premixes from AFFF agents and to fill the rest up to 100%. Very hard water are stored for longer periods).

15

628 247

Buffer systems (if a certain pH value has to be maintained for a long time).

Antifreeze (if AFFF agents must be stored and used at frost temperatures).

Polymeric thickeners (if higher viscosities of the AFFF agents / water premixes are desired due to certain requirements of the dosing system).

The current commercial AFFF agents can only be used in 6% and 3% dosing systems. The composition of the present AFFF agents and the quantity ranges of the different active components of these new AFFF agents are suitable for 0.5 to 12% dosing systems. If you double the concentration of a composition for 6% dosing, you can use such a concentrate for a 3% dosing system. With a 6-fold increase in the concentration of such a 6% dosing system, it can then be used similarly as a 1% dosing system. As comparison values in the examples will show, the preparation of such 1% dosing systems is mainly possible because

A. because the novel Rf surfactants used are more effective and therefore require smaller amounts;

B. because the rather low amounts of solvent required in the new AFFF funds reach the foaming ratios prescribed by the military.

The examples refer to the specifications valid in industry and especially in the military and to our own tests to assess the effectiveness of the claimed compositions. More specifically, the examples refer to the following specifications:

Surface and interfacial tension - ASTM D-1331-56 Freezing point - ASTM D-l 177-65

pH-ASTM D-l 172

Testing the ability to seal

Objective: To measure the ability of a fluorochemical AFFF preparation (at end-use concentration) to form a film over a cyclohexane surface and to seal it.

Procedure: Pipette ten ml of cyclohexane into a 48 mm evaporation dish in an evaporator cuvette. Helium flowing at 1000 cc per minute flushes the cylclohexane vapors from the cuvette through a 3 cm IR gas cell mounted on a PE 257 infrared spectrophotometer (registration infrared spectrophotometer equipped with a time advance). The IR extinction of the gas stream in the area of 2850 cm-1 is continuously monitored while solutions of the preparations are poured onto the surface. The preparations are poured onto the cyclohexane surface at a rate of 0.17 ml per minute using a 1 cc tuberculin syringe driven by a syringe pump with a 13 cm long, number 22 needle, the needle just touching the cyclohexane surface.

The syringe pump is switched on as soon as the absorbance for «unsealed» cyclohexane has been reached. The moment when the very first drop of the formulation solution appears on the surface represents zero time. The time for 50% sealing and the percentage sealing after 30 seconds and after 2 minutes are noted. The time for 50% sealing depends on the film spreading speed (see below), and the percentage sealing after 30 seconds and 2 minutes depends on the effectiveness and performance of the film as a vapor barrier.

Checking the speed of film propagation

Objective: To determine the rate at which an AFFF film spreads across a cyclohexane surface.

Procedure: Fill a 6 cm aluminum bowl half full with cyclohexane and a 50 (xl syringe with a 6% solution of the test solution. 50 fxl of the solution are sprayed down as quickly and carefully as possible along the wall of the bowl so that the solution flow gently onto the cyclohexane surface, cover the dish with an inverted petri dish and start a stopwatch at the end of the injection, observe the spreading of the film over the surface and stop the stopwatch at the moment when the xo film completely covers the surface covered, and noted the elapsed time.

Match check

Goal: Approximate determination of the sealability of an AFFF film.

Procedure: Two thirds of an aluminum weighing pan (58x15 mm) is filled with cyclohexane pro analysi. About 2 ml of AFFF solution to be tested are carefully poured onto the surface. You light a wooden match, and when the initial match flare subsides, you quickly dip the flame through the sealed surface and then pull it out of the bowl. The flame goes out. You repeat this with more matches until you reach persistent ignition, and 25 note the number of matches used.

Fire test

The most critical test for the present compositions is practical fire testing. The details 30 of the procedures for such tests on 2.60 m2, 4.647 m2 and 117.0 m2 fires are in U.S. Navy Specification MEL-F-24385 and their additions.

Process: Premixes of the concentrates according to the invention are prepared from 0.5 to 12% dosing concentrates and tap water or sea water or the AFFF agent is dosed with the aid of a dosing system built into the line. In any case, the test preparation is used in the appropriate concentration.

The effectiveness of the concentrates according to the invention for extinguishing hydrocarbon fires has been repeatedly and reproducibly demonstrated on 2.60 m2 gasoline fires and on 117.0 m2 fires listed on a circular disk with a diameter of 12.19 m. The tests were often carried out under severe environmental conditions with wind speeds of up to 16 45 km per hour and with prevailing summer temperatures of up to 35 ° C. All tests of fire performance as well as additional tests - foaming capacity, film formation, sealability, film spreading speed, viscosity, drainage time, spreading coefficient and so stability - confirmed that the compositions according to the invention did more than the AFFF compositions of the prior art.

The main criteria for determining the effectiveness 55 of a fire fighting composition are:

1. Control Time - The time required to control or control the fire after using the fire extinguishing agent.

2. Extinguishing Time - The time from when the application started until the fire was completely extinguished.

3. Re-ignition time - The time from the complete extinguishing of the flame to the re-ignition of the hydrocarbon liquid in the presence of an open flame on the surface of the liquid.

65 4. Summation of% fire extinguishing - When extinguishing 4.645 or 117.05 m2 fires, the sum of the «percent fire extinguished» is recorded - values at intervals of 10, 20, 30 and 40 seconds. The current regulation for 4,645 m2

628 247

16

- Fire requires a sum of 225 or greater, and for 117.05 m2 - fire of 285 or greater.

2.60 m? Fire test

This test was carried out in a flat round pan made of steel of 0.635 cm thick and measuring 1.83 m in diameter (2.60 square meters) with 12.70 cm high sides, which resulted in about 6.35 cm freeboard during the tests. The pan had no outlets to keep gasoline on a water substrate. A minimal water depth was maintained and only served to ensure that the pan was completely covered with fuel. The agent application nozzle delivered a flow rate of 7.571 per minute at 7.03 kg / m2 pressure. The outlet was modified by a «wing tip» distributor with a 3.175 in. Wide, 4.76 cm long circular arc opening.

The premix solution in fresh water or sea water was 21 ° C ± 5.5 ° C. The extinguishing agent consisted of a 6 percent dosing concentrate or an equivalent amount in fresh water or sea water and the fuel load was 37.851 petrol. The entire load of fuel was poured into the pan over the course of 60 seconds, and the fuel was ignited within 60 seconds of the end of the fuel introduction and allowed to burn freely for 15 seconds before the extinguishing agent was used. The fire was extinguished as quickly as possible by holding the nozzle at a distance of 1.07 to 1.22 m above the ground at such a distance that the nearest edge of the foam could fall onto the nearest edge of the fire. After the fire was extinguished, the extinguishing time was noted, with the distribution of the agent over the test area, until exactly 11.361 premix were used up (90-second application time).

The re-ignition test was started within 30 seconds after the 90 second solution application. A weighted pan with 0.9461 gasoline and a 30.48 cm diameter pan with 5.08 cm side walls was placed in the middle of the area. The fuel in the pan was ignited just before setting it. The re-ignition time started at the moment of this adjustment and ended when 25 percent (0.65m2) of the originally foam-covered fuel surface burned. When the large test pan area maintained flames, the small pan was removed.

117.0 m? Fire test

This test was carried out on a flat, round surface (117.0 m2).

The water depth had the minimum necessary to ensure that the dammed area was completely covered with fuel. The nozzle used to apply the fire extinguishing agent was designed to deliver 189.271 per minute at 7.07 kg / cm2.

The solution in fresh water or sea water had a temperature of 20 ° C ± 5.50 ° C and contained 6.0 ± 0.1% of the composition according to the invention. The fuel consisted of 1 135.61 gasoline. No tests were carried out above wind speeds of 16 km per hour. The entire fuel load was poured into the dike area as quickly as possible. Before the fuel was introduced for a test, all of the extinguishing centers were removed from the pre-emptied area from the previous test.

The fuel was ignited within 2 minutes after the introduction of the fuel had ended and was allowed to burn freely for 15 seconds before the extinguishing agent was used.

The fire was extinguished as quickly as possible by holding the nozzle at a distance of 1.07 to 1.22 m above the ground so that the nearest one

Edge of the foam could fall onto the closest edge of the fire.

At least 85 percent of the fire was extinguished within 30 seconds and the “percent fire extinguished” value 5 was noted.

Manufacturing examples

example 1

N- [3- (Dimethylamino) propyl] -2- or -3- (l, 1,2,2-tetrahydro-io perfluorodecylthio) succinamic acid

C8FI7CH2CH2SCHCOO®

©

CH2CONH (CH2) 3NH (CH3) 2 or 15 ©

C8Fi7CH2CH2SCHCONH (CH2) 3NH (CH3) 2 I

CH2CQO®

20 Maleic anhydride (10.0 g, 0.102 mol) and a mixture of ethylene glycol dimethyl ether (100 g) and N, N-dimethylformamide (60 g) are placed in a stirred, nitrogen-cooled and cooled to 10 ° C. in an ice bath Reaction flask. 3-Dimethylaminopropyl-25 amine (10.4 g; 0.102 mol) is added dropwise over a period of half an hour at a reaction temperature of 10-15 ° C. The resulting white suspension is stirred for one hour at room temperature.

A small amount of this product is dried, washed with heptane and dried under vacuum at 30 ° C for 12 hours. Infrared analysis and NMR signals indicate a connection of the constitution:

COO®

HC

35 II @

HC CONH- (CH2) 3N (CH3) 2 H

N- (3-Dimethylaminopropyl) maleic amide.

40 1,1,2,2-TetrahydroperfIuordecylmercaptan (49.0 g; 0.102 mol) are added all at once into the suspension and the resulting mixture is stirred at room temperature for 64 hours. The thick suspension is filtered and the solids washed with acetone and then dried at room temperature under vacuum 45 µm (0.1 Torr) for 18 hours. The product is obtained as a white powder of 61.2 g in weight (yield = 88.2%) and melting point 123-128 ° with slow decomposition (gas evolution) over the melt. The infrared spectrum agrees with the constitution, in particular the amide band at 1650 cm-1 in solid phase and at 1660 cm-1 in dilute chloroform solution, as well as the asymmetrical or symmetrical carboxylate expansion bands at 1550 cm-1 or 1320 to 1390 cm- ' . The NMR spectrum is in accordance with the constitution and gives the following signals:

55 ©

2.68 ppmN-CH3; 1.8-2.1 NCH2CH2CH2N CH3

60 The surface tension (y0) of the aqueous solution of the above compound is 19.8 dynes / cm. In this and the following examples, the surface tension is measured at a concentration of 0.1% in water at 25 ° C. using a Du Nouy tensiometer.

65

Example 2

N- [3- (Dimethylamino) propyl] -2- or -3- (l, l, 2,2-tetrahydro-perfluoroalkylthio) succinamic acid

17th

628 247

RfCH2CH2SCHCOOe

'©

CH2CONH (CH2) 3NH (CH3) 2

as well as their isomer.

Maleic anhydride (100 g; 1.02 mol) and N-methylpryrrolidone (400 g) are stirred under inert gas in a reaction flask cooled to 0 ° C. in an ice / salt mixture, and the mixture is added dropwise at 0-10 ° C. for 40 minutes with Methyl pyrrolidone (100 g) dissolved 3-dimethylaminopropylamine (106 g; 1.04 mol). The dark brown suspension is stirred for 20 minutes at room temperature and then mixed with methanol (800 g), whereupon the resulting light liquid suspension is heated to 45 ° C. 1,1,2,2-tetrahydroperfluoroakylmerkap-tan (483 g; 0.94 mol) (mixture of compounds with different perfluoroalkyl groups as follows: C6-25%; Cs-50% and C10-25%) is added within 10 minutes 45-50 ° C added, which gives an amber solution, which is stirred at 45 ° C for 3 hours. The completeness of the reaction is demonstrated by the disappearance of the perfluoroalkylethyl mercaptan except for trace amounts in the reaction mixture, as proven by gas chromatography. The identity of the product is confirmed by the infrared absorption for the amide function at 1655 cm "1, and carboxylate can be seen at 1560 cm-1 and 1325-1400 cm. The NMR proton signals obtained are essentially identical to those from Example 1. The compound melts at 95 ° to 115 ° C. The surface tension of the aqueous solution of said compound is 17.7 dynes / cm.

15 According to the procedure described above, compounds analogous to Example 2 are prepared from maleic anhydride and the specified starting materials:

Example No. rf-thiol

Cation-active compound

Yo (dyn / cm)

C8F17C2h4Sh h2n-n;

ch-s

■ CH,

20.6

c8f17c2h4sh h2n-ch2ch2-n;

-c2h5

-c, h,

17.3

C8Fi7C2H4SH HN-CH2CH2CH2-N

CTL

/ -

CH3

sh

20.4

ch2-ch2

c8f17c2h4sh h2n-ch2ch2ch2-n ^ j; o 19.4

^ ch2-CH2 ^

c8f17c2h4sh h2n-ch2ch2-n;

.ch,

"Ctt,

17.9

Example 8

N-methyl-N- (2'-N ', N'-dimethylaminoethyl) -2- or -3- 45

(1,1,2,2-tetrahydroperfluoroalkylthio) succinamic acid

RfCH, CH, S-CHCOO0

©

ch2con-ch2ch2nh

!

ch3

ch3 ch3

and isomer

50

CH2COO

e

Rf is a mixture of C6F13 (25%), C8F17 (50%) and C10F21 (25%).

55

Powdered maleic anhydride (0.033 mol, 3.24 g) is added in portions to a cooled solution of (N, N ', N'-trimethyl) ethylene-1,2-diamine (0.033 mol, 3.47 g) in eo 6 , 7 g of water. The reaction is carried out under nitrogen and kept at 10-20 ° C. using an ice bath. When the addition is complete, the bath is removed and the reaction mixture is stirred at room temperature for 12 hours.

A small amount of solution is dried in vacuo at 30 ° C for 12 hours. A dry, white powder is obtained, the NMR signals of which constitute a compound of the constitution:

65

mark. Acidic hydrogen that can be titrated is not available.

The light yellow solution is mixed with 2-methyl-2,4-pen-tanediol (20.13 g) and then with perfluoroalkylethyl mercaptan (0.3135 mol, 14.65 g). The resulting white suspension is heated to 90 ° C. with stirring until the reaction is complete (6.5 hours). The clear light yellow solution is cooled to room temperature and diluted with water (23 g) to 30% solids. The cloudy solution is filtered clear (asbestos pad with 5 [i porosity) and gives 66.5 g (93.4%) clear light yellow solution. Infrared analysis agrees with the constitution. The surface tension (y0) of the aqueous solution of the above compound is 18.3 dyn / m.

628 247

18th

Example 9 methyl) ethylene 1,2-diamine (0.033 mol, 2.90 g) in 6.7 g water

According to the above regulation, one makes from meleanic acid. The reaction is carried out under nitrogen and

drid, RfCy ^ SH and N, N-dimethyl-N'-ethyl-ethylene-1, 2-third ice bath kept at 10-20 ° C. When the addition is complete,

amine the compound N-ethyl-N- (2'-N'N-dimethylamino- if the bath is removed, the reaction mixture is stirred in overnight

ethyl) -2 or. -3- (l, l, 2,2-tetrahydroperfluoroalkylthio) succin 5 room temperature and adds 2-Me- to the light yellow solution

amic acid. The surface tension of this compound thyl-2,4-pentanediol (20.13 g) and then with perfluoroalkyl-

is 20.2 dynes / cm. ethyl mercaptan (0.3135 mol, 14.65 g). To complete the reaction, the resulting white suspension is 6.5 hours

"_,, Example 10 heated to 30 ° C with stirring. You cool the light yellow

N- (2-Dimethylaminomathyl) -2- or -3- (l, l, 2,2-tetrahydroper- ^ solution to room temperature and diluted with water on fluoroalkylthio) succina.midic acid 30% solids. You filter through an asbestos pad

RrHrH (! R „„ nr.Q 5 n porosity and receives 66.5 g (93.4%) clear light yellow solution.

f 2 2 = 5 ricuu The surface tension of the aqueous solution of the above connections

/ 3 jt manure is 22.0 dynes / cm.

CH2CONHCH2CH2-N-H:

and isomer ch,

15

Powdered maleic anhydride (0.033 mol, Example 10, analogous compounds of maleic anhydride) is added to the procedure described above

3.24 g) in portions to the cooled solution of (N, N-Di- and the starting materials given below:

Example No.

rf thiol

Cation-active compound y0 dyn / cm

11

12

13

RfC 2H4SH

R [C2H4SH

RfC2H4SH

hn-ch2ch2-n.

I.

C2H5

hn-ch2ch2ch2-n I

C2H5

c2H5 C2HS ^ ch3

\

CH,

-C, H,

H2N-CH2CH2CH2-N '

2n5

\

21.3

21.5

18.8

c2h5

14

RAH4SH

hn-ch2ch2ch2-n

c2h5

\ c, H.

CH,

2rl5

21.2

15

- NH,

CgF17C2H4SH J jf

17.9

16

C8F1VC2H4SH CH2NH2

21.4

17th

18th

19th

CgF17C2 H4SH HN H jN-CH3

c8f17c2h4sh. nh2

NH,

C8F17C2H4SH

CO

22.4 16.0

27.4

19th

628 247

Example No.

20th

21st

rf-thiol c6f13c2h4sh c6f13c2h4sh

Cation-active compound

CH3NHCH2CH2CH2NH2 H2NCH2CH2CH2NH2

Y "dynes / cm

18.3 17.2

Example 22

2- or -3- (l, 1 ^ é-tetrahydroperfluorodecylthioibernsteinsäure-mono-fèÇNyN-dimethytyaminoâthylJ-ester

C8F17CH, CH, SCHCOOq ch2cooch2ch2nh;

.ch3 • ch3

and isomer

N, N-Dimethylaminoethanol (0.0408 mol, 3.64 g) in acetone (10 g) is added at 10 ° C. with the solution of maleic anhydride (0.0408 mol, 4.00 g) in acetone (15 g) . The product precipitates as an acetone-insoluble resin. After 30 minutes, methanol (20 g) is added to form a dispersion. 10 1,1,2,2-tetrahydroperfluorodecyl mercaptan (0.0408 mol, 19.6 g) are added, a clear solution forming as the reaction proceeds. The batch is left to stand at room temperature for 24 hours. The gas and thin layer chromatogram (GC and DSC) show no unreacted Merkap-15 tan. Drying the yellow solution in vacuo gives a light yellow wax. The yield is 26.5 g (98.5%).

The surface tension (y0) of the aqueous solution of the above compound is 16.3 dynes / cm.

According to the procedure described above, 22 compounds analogous to Example 20 are prepared from maleic anhydride and the starting materials given below:

Example No.

23

24th

25th

26

Rf thiol

QFnC ^ SH c8fi7c2h4sh

Cation-active compound

CH3-N (CH2CH2OH) 2 HO-CH (CH3) -CH2N (C2H5) 2

c8f17c2h4sh ho-ch2ch2-n

<Ö>

c8f17c2h4sh ho-ch2ch2

<h]

Yo dyn / cm

19.0 17.8

17.4

17.4

Ci8H37 I

27 C8F17C2H4SH H (OCH2CH2) y-N- (CH2CH20) XH 26.3

x + y = 15

28 C6F13C2H4SH HO-CH2CH2-N-CH2CH2-OH 21.2

I.

ch2

I.

h5c2o-p-oc2h5

II

O

Example 29 50 would remove the dry ice / acetone bath and leave that

2- or -3- (l, l, 2,2-tetrahydroperfluorodecylthio) succinic acid reaction mixture slowly warm up to 20 ° C. Then mono- (2'-quinolineethyl) ester is mixed with 1,1,2,2-tetrahydroperfluorodecyl mercaptan

CF CH CH S-CHCOO® (0.0255 mol, 12.24 g). The brown solution turns on overnight

8 17 2 2 1 room temperature and then open for 2 hours

CH2COOCH2CH2->

55 heated to 26 ° C. DSC and GC show no unreacted and isomer mercaptan. The solution is dried in vacuo and obtained

18.2 g light brown powder (94.8%).

The surface tension (yo) of the aqueous solution above

“» R j 1N named connection is 22 dynes / cm.

The stirred solution of 2- (2-hydroxyathyl) -

quinoline (0.0255 mol, 4.2 g) in dichloromethane (20 g) with the

Solution of maleic anhydride (0.0255 mol, 2.5 g) in Di-Example 30

chloromethane (10 g), the mixture cools to 0 ° C. and holds the N, N-bis [(n-propyl-3) -2- or -3- (l, l, 2,2-tetrahydroperfluoro-

Mixture at -10 ° C during addition. After the end of zuctylthio) succinamic acid monoamidojpiperazine

65

628 247

20th

CfiF, iCH, CH, S-CH-COOq

0ooc-ch-s-ch, ch2c6f13

ch2c nhch2ch2ch2n ii o and isomer.

A maleic anhydride solution (0.0510 mol, 5.0 g) cooled with dry ice / isopropanol is added dropwise at -10 to 0 ° C with 1,4-bis (3-aminopropyl) piperazine (0.0255 mol, 5.1 g) ) in 10 g acetone. A white precipitate separates out immediately, and the reaction mixture is stirred at 20 ° C. for one hour.

1,1,2,2-tetrahydroperfhioroctylmerkap-tan (0.0510 mol, 19.27 g) is added and the mixture is stirred for 3 days at room temperature until DSC shows no traces of unreacted r ^ H

iCH2CH2CH2NCCH2 Hll o

Merkaptan's shows more. Drying the amber-colored solution in a high vacuum gives 29.1 g of yellow powder (99% yield).

io The infrared spectrum agrees with the constitution.

The surface tension (y0) of the aqueous solution of the above compound is 22 dynes / cm.

Example 31

15 N- [3- (Dimethylamino) propyl] -2- or -3- (heptafluoroisopropropoxy-l, l, 2,2-tetrahydroperfluoroalkylthio) succinamic acid

CF-!

CF,

CFO (CF2) nCH2CH2S-CH-COO®

CH,

-CONHCH2CH2CH2NH ^

CH,

and isomer

Maleic anhydrides (0.0255 mol, 2.5 g) are dissolved in 10 g acetone and 3-dimethylaminopropylamine (0.0255 mol, 2.61 g) is added dropwise in 5 g acetone in such a way that the reaction temperature at 5- 10 ° C is maintained. As the reaction proceeds, an acetone-insoluble resin is formed; When the amine addition is complete, 10 g of methanol are added to form a uniform mixture.

Heptafluoroisopropoxy-l, l, 2,2-tetrahydro-perfluoroalkyl mercaptan (0.0255 mol, 14.60 g) is added and the reaction mixture is stirred for 2 days until DSC no longer shows any traces of mercaptan. Drying the pale yellow solution in vacuo gives 18.9 g of white powder (95.9% yield).

The infrared analysis agrees with the above constitution.

Example 32

N - [- 3 (Dimethylamino) propyl] -2- or -3- (l, l, 2,2-tetrahydro-perfluorooctylthio) methylsuccinamic acid c6f13ch2ch2s-ch2 i ch-coo0

i © .ch3

ch2-conhch2ch2ch 2nh and isomer ch3

The cooled solution of itaconic anhydride (0.025 mol, 2.80 g) in 10 g of acetone is added at 5-10 ° C. with 3-dimethyl

CH,

25th

35

aminopropylamine (0.25 mol, 2.55 g) in 5 g acetone. An immediate exothermic reaction takes place and the light brown product slowly precipitates. To dissolve the product, 10 g of methanol are added and the reaction mixture is stirred for one hour.

1,1,2,2-TetrahydroperfIuoroktylmerkap-tan (0.025 mol, 9.45 g) are added and the mixture is stirred for 2 days at room temperature. DSC shows no unreacted mercaptan. Drying the clear amber solution in vacuo gives 14.0 g yellow wax (94.6% yield).

The infrared analysis agrees with the above constitution.

40

Example 33

This example illustrates the preparation of sulfonates by quaternization with propane sultone.

41.7 g (0.061 mol) of the surfactant prepared according to Example 1 are dissolved in the same amount of acetone, 7.45 g (0.061 mol) of propane sultone are added, and the reaction mixture is stirred at 50 ° C. for 8 hours; the IR spectrum shows a strong new band at 1035 cm-1, indicating sulfonate formation; a C = 0 band at 1660 cm-1 and bands at 1780 and 1710 cm-1 indicate a certain imide formation. No carboxylate and dimethylamino groups are visible in the IR spectrum, 50 which is generally consistent with the constitution shown below. The product is waxy solid and gives a highly foaming aqueous solution.

CKF17CH2CH2-S

CH,

H

-c-cooh i i ch2-con -ch2ch2ch2-n — ch2ch2ch2s03e h i®

ch3

and its isomer. Elemental analysis: Calculated: Found:

C N S 33.6 3.4 7.6 33.1 3.5 8.0

F

39.6

38.7

The surface tension (y ") of the aqueous solution of the above compound is 21.5 dynes / cm.

60 When heated to 120 ° C for 30 minutes, their IR spectrum changes. The gang at 1660 cm! disappears completely and the two imide bands at 1780 and 1720 cm ~ 1 become very strong; there is no carboxylate and no dimethylami-6s no absorption. This IR spectrum is in accordance with the constitution:

21st

628 247

c8f17ch2ch2-s-ch-c

o ch3

'©

i x N-ch2ch2CHz-n — ch2ch2ch2so3-ch2-c / i

% ch3

O

The surface tension (y0) of the aqueous solution above-cinamic acid from Example 16. The sulfonate (A) forms the slightly named compound is 22.5 dynes / cm. and represents a waxy, brown solid.

10 heat imidation to connect the constitution (B) Example 34 takes place:

Example 33 is repeated with the R-substituted sucrose

c8f, 7ch2ch2-s-ch

CO OH

h, c.

conh-ch ^ n.-ch.chäso, ® (a,

Heat c8f17ch, ch, -s-ch-

i h, c-

\

n-ch2 <

<Ö>

: n®-ch2ch2ch2so3ö (b)

O

The surface tension (yQ) of the aqueous solution above is also present. The spectrum is in agreement with the named connection is 19.1 dynes / cm.

The IR analysis of (A) and (B) is in accordance with the stated constitutions.

Elemental analysis of (B):

c n s f

Calculated: 33.4 3.4 7.7 38.8

Found: 34.6 3.3 8.1 37.2

(B)

Example 35

This example illustrates the formation of R-substituted suc-cinimids from the corresponding succinamic acid.

The IR analysis of the compound prepared in Example 1 shows a strong carboxylate band at 1600 cm-1 and a strong 45 Found: ke C = 0 band at 1660 cm-1 in accordance with the

Constitution:

"QF ^ OVS-Ç-C ^

CH2-C ^ CH3

2 * o

N- (N ', N -Dimethyl-3-aminopropyl) -2- (l, l, 2,2-tetrahydrohep-40 tadecylfluorodecyl) succinimide.

Elemental analysis for (B):

c n s f

Calculated: 33.4 4.1 4.7 47.5

34.2 4.0 5.3 46.4

ions:

H

C8F17-CH, CH2-S-C-COOe

CH2-CO-N-CH2CH2CH2N (CH3)

h h

or

The following examples describe the preparation of further quaternary derivatives.

50 Example 36

2.04 g (0.003 mol) of [2- or -3- (l, l, 2,2-tetrahy- (A) droperfluorodecylthio)] - N, N-dimethyl (3-aminopropyl) succinic acid are dissolved (from Example 1) in 5 cm3 of 35% aqueous HCl, the clear solution is evaporated and the residue is dried under a vacuum (0.1 Torr) at 80 ° C. for 12 hours, giving 2.1 g of white powder of the following constitution receives:

h c8f17-ch2ch2-s-c-coh-ch2ch2ch2n (ch3),

I I

ch2-coo® h

(A ')

cof, 7ch, ch, sch-cooh

60

CH2-CONH-CH2CH2CH2N (CH3) 2H CIe and isomer.

The surface tension (y0) of the aqueous solution of the above compound is 18.8 dynes / cm.

When heated to 120 ° C for 20 minutes, this material foams weakly; it becomes insoluble in water, but dissolves in an acidic aqueous medium. His IR analysis shows two strong,

bands characteristic of cyclic imide at 1780 and 1710 65

cm while the bands at 1600 and 1660 cm-1 are too black. Example 37

Chen shoulders are reduced; strong, for the dimethylamino- melt 2.04 g (0.003 mol) at 123-128 ° C

characteristic absorption at 2770 and 2820 cm-1 zender 2- or -3- (l, l, 2,2-tetrahydroperfluorodecylthio) -N, N-

628 247

22

dimethylaminopropylsuccinamic acid together with 0.43 g (0.003 mol) of methyl iodide in 10 g of isopropanol in an ampoule, heated for 3 hours, filtered the pale pink suspension and dried, giving 1.6 g of white powder of the following constitution melting at 205-250 ° C. :

C8F17CH2CH2S-CH-C

ch2-c

\

NCH2CH2CH2N (CH3) 3 iO

O

The surface tension (y0) of the aqueous solution above. named connection is 24.9 dynes / cm.

Example 38

5 2.04 g (0.003 mol) of 2- or -3- (1,1,2,2-tetrahy-droperfluorodecylthio) -N, N-dimethyl (3-aminopropyl) -succinamic acid are heated with 0.38 g (0.003 mol) of benzyl chloride in 10 g of ethanol under reflux until basic tertiary amine can no longer be detected. The solution is evaporated and gives 2.17 g of whitish semi-solid mass of the constitution

O

©

c8f17ch, ch2sch-c i ^ nch2ch2ch2n (ch3) 2 ch2-ch, -c <

he

^ o

The surface tension (y0) of the aqueous solution of the above compound is 20.8 dynes / cm.

Example 39

2.04 g (0.003 mol) [2- or -3- (1,1,2,2-tetrahy-droperfluorodecylthio)] - N, N-dimethyl (3-aminopropyl) succin

amic acid overnight with 0.28 g (0.003 mol) chloroacetic acid in 2Q 30 g water. Free tertiary amine is undetectable. For defoaming, 20 g of methanol are added and the clear solution is evaporated in vacuo at 60 ° C., giving 2.1 g of whitish wax of the following constitution:

©

. O

c8f17-ch2ch2sch-c r i \ nch2ch2ch2n (ch3) 2ch2coo®

ch2-c \

^ o

The surface tension (y0) of the aqueous solution of the above compound is 17.4 dynes / cm.

Example 40

2.04 g (0.003 mol) of [2- or -3-1,1,2,2-tetrahydropluorodecylthio] -N, N-dimethyl (3-aminopropyl) succin

35

amic acid in 30 ml ether and added dropwise within 5 minutes at 15 ° C with the solution of 0.22 g (0.0031 mol) ß-propiolactone in 5 ml ether. The mixture is stirred at 30 ° C. for 2 hours and the ether is removed on a rotary evaporator. Yield: 2.2 g of a product of the constitution:

C8F17CH2CH2S-CH-COOH

'® o

CH2-CONHCH2CH2CH2N (CH3) 2CH2-CH2COO®

and isomer.

The surface tension (y0) of the aqueous solution of the above compound is 22.6 dynes / cm.

Application examples Table 1

Amphoteric fluorinated surfactants used in Examples 41-117

Amphoteric name

RrTensid

AI

A2

N- [3- (Dimethylamino) propyl] -2- or -3- (l, 1,2,2-tetrahydroperfluoroalkylthio) succinamic acid

N-methyl-N- (2'-N ', N'dimetftyl-aminoethyl) -2-or. -3- (l, l, 2,2-tetrahydroperfluoroalkylthio) succinamic acid

Formula rfch2ch2sch (c02) ch2c0nh (ch2) 3nh (ch3) 2 or +

rfch2ch2sch (ch2c02) c0nh (ch2) 3nh (ch3) 2

rfch2ch2sch (c02) ch2con (ch2) 2nh (ch3) 2

I.

ch3

A3

N-ethyl-N- (2'-N ', N'-dimethylaminoethyl) -2-or. -3- (l, 1,2,2-tetrahydroperfluoroalkylthio) succinamic acid rfch2ch2sch (c02) ch2con (ch2) 2nh (ch3) 2

I.

QHs

A4

N-methyl-N- (2'-N ', N'-dimethylaminopropyl) -2-or. -3- (l, l, 2,2-tetrahydroperfluoroalkylthio) -suc-cinamic acid rfch2ch2sch (c02) ch2c0n (ch2) 3nh (ch3) 2

ch,

23

628 247

Rf is a mixture consisting mainly of QFi3> C8F17 and Q 0F21 approximately in a ratio of 1: 2: 1 and isomers as in Example No. AI. Surfactants A1 to A8: 30% by weight solutions of the 100% active individual homologues in a solvent mixture of 2 parts of hexylene glycol and 3 parts of water.

Table 1 (continued)

Amphoteric name formula

RF surfactant

A 5 A6 A7 A 8

N- [2- (DiethyIamino) ethyl] -2 (3) - (1,1,2,2-tetrahy-droperfluorodecylthio) succinamic acid N- [3- (Dimethylamino) propyl] -2 (3) - (l, l , 2,2-tetra-hydroperfluorooctylthio) succinamic acid N- [3- (DimethyIamino) propyI] -2 (3) - (l, l, 2,2-tetra-hydroperfluorodecylthio) succinamic acid N- [3- (Dimethylamino) propyl] -2 (3) - (l, l, 2,2-tetra-hydroperfluorododecylthio) siccinamic acid

Table 2

Anion-active fluorinated surfactants used in Examples 41-117

Anion-active name

RF surfactant

QF17CH2CH2SCH (COL) CH2CONH (CH2) 2NH (C2H5) 2 C6Fi3CH2CH2SCH (C02) CH2CONH (CH2) 3NH (C H3) 2 C8FI7CH2CH2SCH (C02) CH2C0NH (CH2) 3NH (CH3) 2 C10F2iCH2CH2SCH (CO2) CH2CONH (CH2) 3NH ( CH3) 2

Formula 100%, or as specified, active

B1 B2

B3 B4

B5 B6 B7 B8

Perfluoroalkanoic acid potassium perfluoroalkanoate 25%

2,2-DihydroperfIualkanoic acid

Sodium l, l, 2,2-tetrahydroperfluoroalkylthiopropane

sulfonate

Rf = C6 C8 C10

Perfluoro-heptanoic acid Perfluoronanoic acid

Perfluorun-decanoic acid

Potassium perfluoroheptanoate

75 25 0 4 87 9 0 11.5 88.5

RfC02H

RfC02K - 25% in 10% hexylene glycol / 15% t-butyl alcohol / water RfCH2C02H

RfCH2CH2S (CH2) 3S03Na c6f13co2h c8f17co2h c10f21co2h c6f13c02k - 25% as in B2

x with Rf typically as a mixture of C6F13 (32%), C8FI7 (62%) and C10F2i (6%) as well as traces of other homologues

Table 3

Ionogenic (and amphoteric) surfactants used in Examples 41-117

Ionic surfactant cl C2

C3

C4

C5

C6

C7

C8

C9

cio cll

C12

Type A - anionic K - cationic AM - amphoter

AM AM

AM K

AM AM AM AM AM AM A

AT THE

Name - Active% as specified or ~ 100%

Trimethylamine laurimide

Partial sodium salt of N-lauryl-ß-iminodi-propionic acid (30%)

N-lauryl-myristyl-ß-aminopropionic acid (50%)

Cocosimidazolinium ethosulfate

Dimethyl (2-hydroxypropyl) amine laurimide

Dimethyl (2-hydroxypropyl) amine myristimide

Dimethyl (2-hydroxypropyl) aminpalmitimide

Trimethylamine myristimide

Acylamidoammonium sulfonic acid betaine (50%)

Amphoteric dicarboxylated laurinimidazolinium derivative (38%)

Sodium salt of ethoxylated lauryl alcohol sulfate (27%)

Disodium salt of N-lauryl-ß-iminodipropionic acid

Table 4

Nonionic surfactants used in Examples 41-117 Nonionic Name

Active% as specified or —100%

Surfactant

Dl D2

Octylphenoxypolyethoxyethanol (12) 99% polyoxyethylene (23) lauryl ether

D3 D4 D5

65 D6

D7 D8

Octylphenoxypolyethoxyethanol (16) 70% octylphenoxypolyethoxyethanol (10) 99% octylphenoxypolyethoxyethanol (30) 70% nonylphenoxypolyethoxyethanol (20) nonylphenoxypolyethoxyethanol (30) 70% branched alcohol ethoxylate (15)

The numbers in parentheses mean recurring ethylene oxide units.

628 247

24th

Table 5

Solvents used in Examples 41 to 117 Solvent Name

El

E2

E3 E4 E5 E6

1-butoxyethoxy-2-propanol

1-butoxy-2-propanol / 2-methyl-2,4-pentanediol in a ratio of 2: 3 diethylene glycol monobutyl ether

2-methyl-2,4-pentanediol

Tetrahydrothiophene-1,1-dioxide ethylene glycol

Examples 41 to 44 The composite AFFF agents as shown in Table 6 have identical compositions, except that the Rf group in the amphoteric RrTensid from a pure perfluorohexyl over a pure perfluorooctyl to a pure

Perfluorodecyl group and a mixture of perfluorohexyl, perfluorooctyl and perfluorodecyl in an approximate ratio of 1: 2: 1.

As the surface tension data in Table 6 shows, 5 the lowest values are obtained with the pure C8 isomer, followed by the amphoteric Rf surfactant with mixed Rr groups. On the other hand, the lowest interfacial tension values are obtained with the C6 isomer and the Rr isomer mixture. As a result, the highest spread ic coefficient of 6.5 dynes / cm is achieved with the Rr mixture. Rf-mixed amphoteric fluorinated surfactants of type A with mixed Rf groups are of course highly desirable from the standpoint of economy.

Unless otherwise stated, the pH values of the compositions in this and the following examples are generally in the range from 7 to 8.5.

Table 6

Effect of the amphoteric Rr surfactant (component A) and its homolog content Example Nos. 41 to 44

Various amphoteric surfactant solutions: (as indicated)

Anionic Rr surfactant

Bl:

0.29%

Amphoteric auxiliary surfactant

C2:

8.33% (30% solids)

Another auxiliary surfactant

C4:

0.83%

Non-ionic auxiliary surfactant

D2:

2.08%

solvent

El:

5.00%

water

rest

Example No.

41

42

43

44

RrTensid A6,30% as present

4.93

RrTensid A7,30% as present

4.93

RfTensid A8,100% as present

1.48

Rf surfactant AI, 30% as present

4.93

Surface tension "dyn / cm

17.7

16.9

18.0

17.2

Interfacial tension * dyn / cm

0.9

1.7

1.7

0.9

Spreading coefficient "dyn / cm

6.0

6.0

4.9

6.5

* Diluted to 3 percent with distilled water; Border

surface tension against cyclohexane

Examples 45 to 50 The AFFF agent compositions listed in Table 7 are of identical composition, with the exception of the anion-active fluorinated surfactants of type B, which change from a perfluorohexyl via a perfluorooctyl to a perfluorodecyl group, such as mixtures as in Table 2 defined Rr groups are modified. The lowest surface tension data is obtained with perfluorooctyl and a mixed perfluoroalkyl group containing nonionic surfactants of type B. These preferred compositions also show the highest film spreading rate.

The most important of the results given in Table 7 is the fact that an AFFF agent containing no anion-active fluorinated type B surfactant has significantly higher surface tensions, and therefore a lower spreading coefficient, no film sealing properties and additionally a very slow film spreading speed.

Examples 51 to 57 The measurements of the surface properties shown in Table 8 show that aqueous solutions of amphoteric Rp surfactants of type A have low surface tensions but high interfacial tensions (measured against hydrocarbons such as cyclohexane), and such aqueous solutions therefore have negative spreading coefficients. The addition of amphoteric auxiliary surfactants of type C to aqueous solutions of amphoteric Rr surfactants of type A er-55 makes it possible to lower the interface properties and to achieve these very high spreading coefficients. Type C amphoteric auxiliary surfactants are therefore referred to as interfacial tension reducers, although they contribute to other properties of the AFFF agents such as foaming, stability, etc. Examples 51 to 56 show how the interfacial tension of a 0.1% aqueous solution of the amphoteric RrTenside A5 by adding the preferred fatty acid aminimide surfactants of type C listed in Table 3 from 7.1 dynes / cm to below 1, 0 dynes / cm is reduced; the spreading coefficient increases from - 1.1 dynes / cm to 5.6 dynes / cm. A typical non-ionic surfactant D4 is much less effective.

60

25th

628 247

Table 7

Effect of the anion-active Rp surfactant and its homolog content Example Nos. 45 to 50

Amphoteric Rf surfactant solution

AI: 4.93% (30% solids)

Anionic RrTensid Various: 0.29%

Amphoteric auxiliary surfactant

C2: 8.33% (30% solids)

Another amphoteric auxiliary surfactant

C3: 1.66% (70% solids)

Non-ionic auxiliary surfactant

D3: 2.97% (70% solids)

solvent

El: 5.00%

water

rest

Example No.

45 46

47

48

49

50

Anionic Rf surfactant as indicated without B5

B6

B7

B1

B3

RpHomolog c6

c8

Qo

Mixture mixture

Surface tension * dyn / cm

19.5 18.1

17.5

17.7

17.7

17.5

Interfacial tension * dyn / cm

1.0 0.6

1.2

1.7

1.0

1.0

Spreading coefficient * dyn / cm

4.1 5.9

5.9

5.2

5.8

6.1

Film propagation speed, sec

very 13

5

38

9

slowly

Reseal property no good good bad good good

* Diluted to 3 percent with distilled water; Interfacial tension against cyclohexane Table 8

Surface properties of amphoteric RrTensid- /

amphoteric auxiliary surfactant solutions Amphoteric RF surfactant solution A5: 0.1%

Auxiliary side - various 0.1%

Water rest

example

Auxiliary surfactant

surfaces

Interfaces

Spreading

voltage voltage coefficient

dyn / cm dyn / cm

51

without

18.6

7.1

-1.1

52

C5

18.4

0.6

5.6

53

C6

18.8

0.6

5.2

54

C7

20.2

0.2

4.2

55

Cl

18.6

0.9

5.1

56

C8

19.3

0.5

4.8

57

D4

19.6

3.8

1.2

Examples 58 to 63 The AFFF compositions with a composition as shown in Table 9 are identical, with the exception of various non-ionic aliphatic auxiliary surfactants of type D. Comparison of the surface tension and interfacial tension data shows that one is almost identical down to 0.5 dyn / cm

Values are preserved and all samples have excellent compatibility with sea water, while the only sample containing no non-ionic hydrocarbon surfactant of type D gives a strong precipitation when diluted with sea water and aged for 10 days at 65 ° C.

Table 9

Composition and assessment of AFFF agents Example Nos. 58 to 63

Amphoteric surfactant solution AI

Anion-active RrTensid B1

Amphoteric's auxiliary surfactant C2

Additional amphoteric auxiliary surfactant C3

Non-ionic auxiliary surfactant

solvent

water

Different El:

4.93% (30% solids) 0.29%

8.33% (30% solids 1.66% (50% solids) 2.08% (as 100% solids) 5.00%

rest

628 247

26

Table 9 (continued)

Example No.

58

59

60

61

62

63

Nonionic auxiliary surfactant as indicated without

D3

D5

D6

D7

D8

Surface tension * dyn / cm

18.0

17.3

17.4

17.0

16.9

17.5

Interfacial tension "dyn / cm

1.7

1.2

1.4

1.3

1.3

1.6

Spreading coefficient * dyn / cm

4.9

6.1

5.8

6.3

6.4

6.0

Compatibility with seawater stronger clear clear clear clear clear when diluted to 6%, 10 days

Low

at 65 ° C

blow

"Diluted to 3% with distilled water; interfacial tension against cyclohexane

Examples 64-78

AFFF agents for 6 percent dosing containing 2 percent by weight of different solvents, but otherwise identical compositions as shown in Table 10, are assessed using the open-air foam test method to determine the foam spread of a 6 percent dilution of the new AFFF agents in synthetic seawater . As the data in Table 10 shows, simply by changing the type of solvent used in the AFFF agent, spreading ratios ranging from 4.0 (high density foam) to 11.0 (lower density foam) can be obtained. It is important from an ecological as well as from an economic point of view that one is so broad

15

Foam spread area can achieve with such a low (2 percent) solvent content.

Table 10

Composition of AFFF funds

Example Nos. 64 to 78

Amphoteric R surfactant solution Anionally active Rf surfactant 'Amphoteric auxiliary surfactant Non-ionic auxiliary surfactant Solvent, various water

AI:

3.07%

Bl:

0.19%

Cl:

3.00%

Dl:

3.00%

2.00%

rest

example

solvent

foam

example

solvent

foam

No.

spread no.

spread

64

Without

4.2

72

Butoxy-2-propanol

11.0

65

Diethylene glycol monobutyl

7.9

73

Dipropylene glycol mono-

5.0

ether

ethyl ether

66

Diethylglycoldiethyläthyer

4.2

74

Propylene glycol mono-

4.1

ethyl ether

67

N-methyl-2-pyrrolidorï

4.1

75

2-methyl-2,4-pentane diol

6.2

68

Tetrahydrothiophene

4.3

76

Propoxy-2-propanol

7.2

1,1-dioxide

69

t-butanol

6.3

77

Dipropylene glycol

4.0

70

N, N-dimethylformamide

5.3

78

l-butoxyethoxy-2-

11.0

propanol

71

N, N-dimethylacetamide

4.5

Examples 79 to 82 AFFF agents with compositions as given in Table 11 are evaluated and compared to a commercially available AFFF agent, Light Water FC-200, in 2.60 m2 fire tests. As the control time, extinguishing time and re-ignition time data show, higher performance can be achieved with the new AFFF agents with a fluorine content in the product reduced by half; compared to FC-200, approximately the same control time, extinguishing time and re-ignition time are achieved with the AFFF agent from Example 82, which contains only 0.8 percent fluorine, compared to 2.1 percent fluorine in FC-200. These results indicate the higher effectiveness of the new AFFF agents and the less importance of foam spread as a performance criterion compared to better film properties.

Table

Comparative fire test data * for AFFF agents Example Nos. 79 to 82

Amphoteric surfactant solution as non-ionic auxiliary surfactant Dl

AI Dl

Anionic RrTensid B1 Amphoteric auxiliary surfactant Cl solvent E2

water

Different Different

1.4

0.35%

2.25%

6.25%

rest

(30% solids) (100% solids)

(based on solids)

(100% solids)

27th

628 247

Table 11 (continued)

Example No.

79

80

81

82

FC-200

Rf-Tensid AI,% as available Non-ionic surfactant Dl,% as available

8.40 1.80

7.00 1.50

5.60 1.20

4.66 1.00

% F in the composition

1.44

1.20

0.96

0.80

2.10

Control time, sec. Deletion time, sec.

Re-ignition time, min.

29 44 8:15

30 34

10:30

34 47 5:45

34 51 4:58

33 52 5:30

Foam spreading drainage time to 25%, min.

5.5 4:42

5.6 4:00

5.4 4:15

4.7 3:45

7.0 5:03

x Diluted to 6% with sea water, tested on 2.60 m2 fire

Examples 83 to 85 20

AFFF agents with the composition solvent-containing AFFF agents shown in Table 12, foams of high tongue and with various Rt surfactants of type B and density with a foam spread of less than 5 and even 3.7, various solvents of type E, or even While a solvent of 35 percent does not foam the solvent, it is assessed by means of 2.60 m2 fire tests using this AFFF composition, except for the 8.5 use of a nozzle for 6.57 liters per minute. 25 height. A comparison with the commercially available FC-200 shows that As the test data in Table 12 show, one does not get somewhat better extinguishing times in Example 83.

Tables

Comparative fire test data x for AFFF agents Example Nos. 83 to 85

Amphoteric Rf surfactant solution AI: 7.1 (30% solids)

Anionic Rf surfactant various (100% solids)

Amphoteric auxiliary surfactant Cl: 3.0 Non-ionic auxiliary surfactant Dl: 3.0 solvent water

Various rest

Example No. 83 84 85 FC-200

R £ anionic surfactant Bl,% as present 0.33 0.33

Anionic Rf surfactant B4,% as in the present 0.50

Solvent E3 35 without without

Sweet sea sweet sea sweet sea sweet sea water water water water

Deletion time, sec.

40

46

55

80

67

83

52

52

Re-ignition time, min.

6:00

6:00

8:44

3:20

8:05

3:27

6: 3

5:30

Foam spread

8.5

7.7

3.8

3.8

4.8

3.7

7.0

7.0

* Diluted to 6 percent with fresh or sea water, tested on 2.60 m2 fire

Examples 86 to 90 The AFFF agents with the composition given in Table 13 are assessed by 2.60 m2 fire tests. The performance of these various AFFF agents containing Type C auxiliary surfactants gives excellent control times (down to 26 seconds) and very short

Extinguishing times (down to 37 seconds) and two of the 60 compositions (Examples 88 and 90) extinguish the fire shortly after removal of the pan used in the 2.60 m2 fire test, which is the superior sealing ability of the new AFFF agents compared to commercially available products.

628 247

28

Tables

Comparison fire test data * for AFFF agents Example Nos. 86 to 90

Ali amphoteric surfactant solution

Anionic Rt surfactant Bl:

Ionogenic (and amphoteric) auxiliary surfactants Non-ionic auxiliary surfactant D1:

Solvent E:

water

5.9% (30% solids)

0.35% (100% solids)

Various

1.2

6.0

rest

Example No.

86

87

88

89

90

Auxiliary surfactant - 1% solids

C3

C4

Cl

Cl

Cl

Auxiliary surfactant — 2% solids

C2

C2

C9

C10

C2

Mastery time, sec

26

27th

33

33

26

Deletion time, sec.

39

37

48

45

38

Re-ignition time, min.

7:31

5:02 from +

7:56

4:35

Foam spread

5.9

6.2

6.7

5.9

6.6

Drainage time to 25%, min.

5:19

5:20

5:05

5:55

* Diluted to 6% with sea water, tested on 2.60 m2 fires + fire extinguished completely

Example 91

An AFFF agent of the composition shown in Table 14 is fired on a 117.05m2 fire set on a flat, 12.19m diameter round surface filled with 1.135m³ of gasoline using a double shielded Rockwool FFF nozzle with an output of 189.271 per minute. Excellent foam spread of 9.0 is obtained; the fire is quickly dampened and is almost completely extinguished within the dike area. The re-ignition is minimal and the "total extinction percent" at 320 far exceeds the military specification F-24385 (US Navy).

Table 14

Fire test of the preferred AFFF agent in the 117.0 m2 fire test example No. 91

Amphoteric surfactant solution AI: 5.93% (30% solids)

Anionic RrTensid Bl: 0.35%

Amphoteric auxiliary surfactant C2: 10.00% (30% solids) Other amphoteric

Surface tension * dyn / cm interfacial tension "dyn / cm spreading coefficient" dyn / cm

30th

17.0 1.4 6.2

Assistant surfactant Cl

Nonionic auxiliary surfactant D1

Solvent water

0.50% 1.20% 6.00% rest

Fire test performance with seawater dilution to 6 percent

Damping and re-ignition awarded "Total Deletion Percentage" - 320

35

Foam spread (189.271 per minute) drainage to 25%

Drainage to 50%

9.0 4:00 8:41

40 "Diluted to 3% with distilled water; interfacial tension against cyclohexane

Examples 92 to 96 AFFF agents of the compositions shown in Table 15 are tested as aerosol-dispensed AFFF agents on 2B fires (name of the Underwriters Laboratory). The results show that the fire extinguishing compositions are more effective in a shorter time than one or the other of the commercially available agents, i.e. Light Water FC-200 50 or FC-206. According to Example 54, a frost-protected composition is also effective as an extinguishing agent.

Table 15

Composition and evaluation of aerosol-dispensed AFFF agents Example Nos. 92 to 96

Example No. 92 93 94

95

96

FC-200 FC-206

A2 A2 AI AI A4 Bl, 0.24 B4.0.34 B2.1.1 B2.1.1 Bl, 0.24

Amphoteric surfactant solution 4.9% as present (30% solids)

Anionic R r surfactant,% as present

Amphoteric auxiliary surfactant,% as in the present case Cl, 3.0 Cl, 3.0 C2.5.0 C2.5.0 C2, 2.0

Additional ionic surfactant,% as above - - - C4.0.5 C4.0.5 C4.0.5

enough

Non-ionic auxiliary surfactant,% as above - Dl, 1.0 Dl, 1.0 Dl, 1.75 Dl, 1.75 Dl, 1.0 gend

29

628 247

Table 15 (continued)

Solvent E4.3% +% others as indicated1

Buffer salts, 0.2%, type as stated 1.3 bottles

Surface tension 4 dynes / cm 18.7

Interfacial tension4 dynes / cm 0.9

Spreading coefficient4 dynes / cm 5.0

Fire performance properties5 made of aerosol can2

Duration of submission, sec. 43

Foam volume, liters 6.7

Mastery time, sec. 20

Deletion time, sec. 54

E5.20.0 -

F3

Fl

F2

F4

-

19.3

18.1

19.6

15.9

16.3

-

1.5

1.9

1.7

4.0

4.5

-

3.7

3.6

3.3

4.7

3.8

; -B6 fires when diluted to 6%

32

52

64

49

58

51

6.5

6.0

7.0

6.5

8th

8th

24th

23

26

21st

19th

23

46

45

34

37

74

59

Note to Table 15

The% solvent contents and% buffer salts are given for the actual aerosol charge after dilution of the concentrate to 6%; the rest is water.

2The aerosol container is a standard can that contains a 430 gram load of AFFF agent and a 48 gram load of dichlorodifluoromethane.

3 The buffer salts are Fl, Sörensen phosphate at pH 7.5 F2, Sörensen phosphate at pH 5.5 F3, Mcllvaine citrate phosphate at pH 5.5 and F4, Walpole acetate at pH 5.5.

4 Diluted to 6.0% with distilled water; Interfacial tension against cyclohexane.

5 Delivery time, seconds - Time until the aerosol is completely emptied at 21.1 ° C foam volume, liters - Total foam volume immediately after delivery Control time, seconds - Time at which the fire is under control, but still extinguishing time, seconds - Time to extinguish completely 62B fire - fire on 0.465m2 area

Examples 97 and 98 35

AFFF agents of the composition shown in Table 16 are used with commercially available AFFF agents of both the 6 percent and 3 percent dosage types - Light Water FC-206 and FC-203 from 3M and Aer-O-Water 6 and 3 from National Foam - compared. Examples 97 and 98 both demonstrate far superior film propagation speeds (time up to 50 percent sealing) as well as more complete and longer lasting seals than available AFFF agents. These factors are of fundamental importance for an effective AFFF composition. 45

Table 16

Sealing properties of AFFF compositions Example Nos. 97 and 98

Amphoteric Rf surfactant solution Anionally active Rf surfactant Amphoteric auxiliary surfactant Additional ionic auxiliary surfactant Non-ionic auxiliary surfactant Solvent water

AI Bl C2

El:

5.0% (30% solids) 0.3%

8.3% (30% solids)

Various

Various

5.00%

rest

Aer-O-Water

Aer-O-Water

FC

FC

Example No.

97

98

6

3rd

206

203

Assistant surfactant Cl

0.4

Auxiliary surfactant C4

-

0.4

Auxiliary surfactant D3

3.0

-

Auxiliary surfactant Dl

-

2.1

Time up to 50%

5

8th

18th

18th

25th

12

seal

% Seal

98

97

45

30th

85

72

in 30 seconds

% Seal

98

98

87

91

96

87

in 120 seconds

surface

Conveyor speed

Wavenumber

Cell length

Helium flow rate

- 20 cm2

- 0.17 ml / min.

- 2 930 cm-1

- 3 cm

- 1,000 ml / min.

628 247

30th

Examples 99-103 AFFF agents of the compositions shown in Table 17 are subjected to fish toxicity studies on Pimephales promelas and Lepomis macrochirus. As the results show, the AFFF funds investigated have considerably lower to-

Table 17

xicity than the control (Light Water FC-200) and also have a significantly lower chemical oxygen demand than the control, mainly because of the lower solvent content in the new AFFF agents.

Composition and assessment of AFFF funds

Example Nos. 99-103

Example No.

99

100

101

102

103

FC-200

Amphoteric Rf surfactants

AI

A2

A3

AI

A4

Type +% as in the present

5.60

5.60

5.60

4.93

4.93

-

Anionic RrTenside

0.24

0.24

0.24

0.24

0.24

-

Bl,% as is

Auxiliary surfactant Cl,% as present

3.00

3.00

3.00

Auxiliary surfactant C2,% as present

-

-

-

8.33

8.33

-

Auxiliary surfactant C3,% as present

-

-

-

1.66

1.66

-

Auxiliary surfactant Dl,% as here

1.50

1.50

1.50

2.08

2.08

- "-

Solvent, type +%

E2

E2

E2

El

El

Butyl carbitol

6.0

6.0

6.0

5.0

5.0

34.0

Fish species

Fish toxicity ppm TL1

484

700

859

611

483

49

(Pimethales promelas) TL50

303

298

327

285

182

16

(Lepomis macrochirus) TL99

190

129

124

133

69

5

312 79 20

COD, g 02 / liter

0.29

0.31

0.29

0.18

0.70

Examples 104-108 AFFF 6 percent dose compositions containing different types of Type C and Type D amphoteric auxiliary surfactants, but otherwise identical compositions are evaluated. The comparative evaluation data in Table 18 show (a) that 3% solutions of the listed AFFF agents have spreading coefficients between 4.5 and 5.8 dynes / cm

35

and (b) the concentrates per se have fish toxicity (Pimephales promelas) between 114 and 524 ppm for TL50, which shows that the AFFF agents listed are significantly less toxic than Light Water FC-200 with a TL50 of 79 ppm. Table 18 also shows that the AFFF agents listed have a significantly lower chemical and biological oxygen demand (COD and BOD5) than FC-200.

Table 18

Composition of AFFF agents Example Nos. 104 to 108 Amphoteric surfactant solution Al: anionic surfactant Bl Amphoteric auxiliary surfactant C2 Other auxiliary surfactants Solvent El:

water

Example No.

4.93% (30% solids)

0.29% (100% solids)

8.33% (30% solids)

Various

5.00%

rest

Auxiliary surfactant Cl,% as in the present case Auxiliary surfactant C3,% as in the present case Auxiliary surfactant C4,% as in the present case Auxiliary surfactant Dl,% as in the present case

104

1.66

105

0.42

106

0.84 2.08

107

0.42 2.08

108

0.84 2.08

FC-200

Auxiliary surfactant D3,% as present

2.97

2.97

- •

-

-

-

Surface tension "dyn / cm

18.0

17.2

18.2

18.4

18.4

15.9

Interfacial tension * dyn / cm

1.5

1.6

1.9

1.4

1.3

4.0

Spreading coefficient dyn / cm

5.1

5.8

4.5

5.2

4.9

4.7

Fish toxicity, ppm TLj

434

880

480

447

160

312

(Pimephales promelas) TL50

294

524

318

228

114

79

TL99

198

313

211

116

82

20th

COD, g 02 / g

0.19

0.20

0.28

0.26

0.25

0.70

BOD5 mg 02 / liter

876

1023

12,300

10,000

5830

15,600

* Diluted to 3% with distilled water; Interfacial tension against cyclohexane

31

628 247

Further optimized AFFF agents for 6 percent dosing, which contain different types and amounts of amphoteric and non-ionic auxiliary surfactants of types C and D, but identical amphoteric and anionic Rr surfactants of types A and B, are assessed. The comparative evaluation data in Table 19 show that spreading coefficients in the range from 3.6 to 5.1 dynes / cm are obtained, while the fish toxicity data of the AFFF medium concentrates extend over a range from 294 to over 1000 ppm as TL5Ü for Pimephales promelas.

ken. A TL50 greater than 1000 ppm is considered non-toxic, and products such as the AFFF agents of Examples 112 and 113 are therefore highly desirable from an environmental standpoint. Table 19 also lists the chemical and biological oxygen demand (COD, BOD5) of Examples 70 to 73. The very low COD values of 0.19 to 0.22 g oxygen per liter result mainly from the low solvent content of the new AFFF agents.

Table 19

Composition and assessment of AFFF agents Example Nos. 109 to 113

Amphoteric Rf surfactant solution AI: 4.93% (30% solids)

Anionic Rf surfactant Bl: 0.29% (100% solids)

Amphoteric auxiliary surfactant and non-ionic

Auxiliary side Various

Solvent El: 5.00%

Water rest

Example No.

109

110

111

112

113

FC-200

Auxiliary surfactant C2,% as present

8.33

8.33

8.33

5.66

5.66

-

Auxiliary surfactant C3,% as present

1.66

1.66

1.66

-

-

-

Auxiliary surfactant Dl,% as here

2.08

-

0.75

-

-

Auxiliary surfactant D2,% as present

-

-

2.08

-

0.75

-

Auxiliary surfactant D3,% as present

-

2.97

-

-

-

-

Surface tension * dyn / cm

18.1

18.0

18.2

18.1

18.2

15.9

Interfacial tension * dyn / cm

1.3

1.5

1.5

2.5

2.8

4.0

Spreading coefficient dyn / cm

5.2

5.1

4.9

4.0

3.6

4.7

Fish toxicity, ppm, TL!

611

434

480

> 1,000

> 1,000

312

(Pimephales promelas) TL50

285

294

318

> 1000

> 1,000

79

TL99

133

198

211

> 1,000

> 1,000

20th

COD, g O / g

0.19

0.22

0.20

0.19

0.70

BOD5 mg O / liter

-

876

906

5,600

6 830

15,600

x diluted to 3% with distilled water; Interfacial tension against cyclohexane

Example 114 50

An AFFF agent is selected which shows the corrosion tests given for example 112, as shown in Table 20, the composition and solutions thereof in synthetic give that the corrosion observed on various metals and alloys in relation to the weak or non-corrosive behavior 10 - up to 100 times smaller than that shown in MIL-the new AFFF funds. According to U.S. Military F-24385, Supplement 8, the maximum allowable requirement MIL-F-24385 Supplement 8.20. June 1974, 55 evaluations.

628 247

32

AFFF agent MIL-F-24385-

Example No. 112 regulation

By- maxi supplement 8

Schnitt2 ^ mum (June 20, 1974)

Corrosion (milligrams / DM day)

A. Metal strips partially in liquid for 38 days

Immersed at 38 ° C

dilution

alloy

Concentrate1)

Cold rolled steel SAE1010

0.16

0.24

25 maximum

concentrate

Stainless steel (CRES 304)

0.2

0.2

25 maximum

6% in sea water

Copper nickel (90% Cu, 10% Ni)

0.42

0.59

10 maximum

concentrate

Aluminum 6061T6

-0-

-0-

Not specified

B. metal strips at ordinary temperature in 60 days

completely immersed in the liquid (0.0254 mm / year)

dilution

alloy

90% in sea water

Cold rolled steel SAE 1010

0.39

0.78

Not specified

90% in sea water

Copper nickel (90% Cu, 10% Ni)

0.33

0.73

Not specified

90% in sea water

Monel 400

-0-

0.05

Not specified

90% in sea water

Bronze 905 (milligrams)

7

8th

Not specified

C. Local corrosion - 60 days of rubber-clad metal strips immersed in liquid at ordinary temperature for 60 days. Thinning alloy

None CRES304 None None None Visible

(stainless chrome-nickel steel) holes holes pitting at 10X at 10X at 10X

Magnification undiluted 2) Average from 4 experiments

Examples 115-117 len. Six percent dosing concentrates such as Aer-O-Water 6

The AFFF agents are prepared with the same ingredients, the National Foam and Light Water FC 200 with a Lö, but in progressively higher concentrations. contain 18% and 34 percent, respectively. The data show that stable and high-performance concen- trates 40 so much solvents that they cannot be prepared as 1 percent dosing controls for 3 percent and even 1 percent dosing concentrates are.

Table 21

Formulation of highly concentrated AFFF agents

Example Nos. 115 to 117

Example No.

115

116

117

Dosage type

6%

3%

1%

% how

%

% how

%

% how

%

in front

Fixed before

Fixed before

Firmly

lying fabrics lying fabrics lying fabrics

Amphoteric surfactant AI

3.33

1.00

6.66

2.00

20.0

6.0

Anionic Rf surfactant B2

0.80

0.20

1.60

0.40

4.80

1.20

Amphoteric auxiliary surfactant C12

1.70

1.70

3.40

3.40

10.20

10.20

Non-ionic auxiliary surfactant Dl

0.50

0.50

1.00

1.00

3.00

3.00

solvent

6.00

-

12.00

-

36.00

water

87.67

- -

75.34

-

26.00

total

100.00

3.40

100.00

6.80

100.00

20.4 fi

Table 20 property

Freezing point ° C PH

Chloride content (ppm)

-3 7.5 <50

-7 7.5> 50

-12 7.5> 50

Claims (7)

628 247 2. Concentrates according to claim 1, characterized in that the anionic fluorinated surfactant B of the formula wherein Rf is a fluorine-containing, saturated, monovalent non-aromatic radical having 3 to 20 carbon atoms, the chain carbon atoms only being fluorine, chlorine or hydrogen atoms with at most a hydrogen or 5 chlorine atom is substituted on two carbon atoms and there can be a divalent oxygen or trivalent nitrogen atom bound only to carbon atoms in the skeleton chain, Qm is an alkylene, sulfonamidoalkylene or carbonamido-io alkylene bridge member, Z is an anionic, water-solubilizing polar group and m is O or 1, (C) the ionogenic fluorine-free surfactant is a carboxylic acid, a sulfuric acid ester, an alkanesulfonic acid or alkyl aromatic sulfonic acid, a phosphate, a phosphonic acid, a thio 15 is sulfate or a sulfinic acid, (D) the non-ionic non-ionic surfactant is a polyoxyethyl derivative of alkylphenols, linear or branched alcohols, fatty acids, mercaptans, alkylamines, alkylamides, acetylene glycols, phosphorus compounds, glucosides, fats 20 and oils, amine oxides or phosphine oxides or is a surfactant derived from block polymers containing polyoxyethylene and / or polyurethane oxypropylene units and (E) the solvent is 1-butoxyethoxy-2-propanol, hexylene glycol or diethylene glycol monobutyl ether. 25 3. Concentrates according to claim 2, characterized in that they (A) 1.0 to 3.5% by weight of an amphoteric fluorinated surfactant, (B) 0.1 to 2.5% by weight of the anionic fluorinated Ten-30 side, (C) 0.1 to 4.0% by weight of the ionogenic fluorine-free surfactant, (D) 0.1 to 8.0% by weight of the non-ionic fluorine-free surfactant and (E) 0 to 20 wt .-% of the solvent and enough 35 water to make up the rest to 100%. 2 ® -R -N 40 is what Y is a radical of the formulas - (CH2) 4-, - (CH2) 5-, - (CH2) 2-0- (CH2) 2- and 45 - (CH2) -CH-N- (CH2) 2-, wherein R2, R5, A® and G® are the © (le) - (R2) —N \ R3 g © R4 represents what R2 is linear or branched alkylene of 2 to 12 carbon atoms, oxygen or sulfur interrupted linear or branched alkylene of up to 60 carbon atoms or hydroxyl-substituted alkylene and k is 1 or zero, with the restriction that k is 1 when X is oxygen , R3 and R4 independently of one another each represent hydrogen, an alkyl group or substituted alkyl group having 1 to 20 carbon atoms, a phenyl group, an alkyl- or halogen-substituted phenyl group having 6 to 20 carbon atoms or a polyethoxy or polypropoxy group having 2 to 20 alkoxy units with the restriction that R3 and R4 are not hydrogen when X is oxygen, and wherein alkyl is 1 to 5 carbon atoms, dienyl, hydroxyl, carboxyl, halogen, alkylene dialkylphosphonate or a group of the formula R7 R8 have given meanings, and R7 and R8 independently represent hydrogen or a lower alkyl 50 or hydroxy lower alkyl group having 1 to 6 carbon atoms, with the restriction that R8 is not hydrogen when X is oxygen; Q is also an aromatic amino group of the formulas 55 60 65 (3a) (3b) Za Za (R \ ^ 0 R ~ © and 2nd -R -ÏT, Y R ~ $ and (2c) 2nd ■ R -N 2nd Claims 1. Aqueous, film-forming concentrates for extinguishing or preventing fire by suppressing the evaporation of flammable liquids, characterized in that they (A) 0.5 to 25% by weight of a non-anionic fluorinated compound of the formula (i) rf-r1 -s- (ch2) v-ch-coo® I. ch2-cox-qh, (ii) rr-r1-s- (ch2) y-ch-cox -qh I. cho-coo® and (III) Rf-R1-S- (CH2) y-CH - C \ O n-q CH2-C O ■ n: , R3 \ r4 s as substituents on alkyl and methyl, halogen or hydroxyl as substituents on phenyl A® is an anion which forms an ammonium salt of the formula NH4® A® and is derived from alkyl halides, benzene or chlorobenzenesulfonate esters of alkyl alcohols and methyl and Ethyl sulfates from-10 conducts, R5 is hydrogen, alkyl or hydroxyalkyl, aralkyl or a group of the formula - (CH2) n-COO-alkyl, in which alkyl contains 1 to 18 carbon atoms, and G® is a group of the formula 15 - (CH2) n-COO®; - (CH2) 3S03®; -CH-COO® or -C-COO® 20th ch2-COOH CH-COOH wherein Rf straight-chain or branched perfluoroalkyl having 1 to 18 carbon atoms or such a perfluoroalkyl substituted by perfluoroalkoxy having 2 to 6 carbon atoms, R1 branched or straight-chain alkylene having 1 to 12 carbon atoms, alkylene thioalkylene having 2 to 12 carbon atoms, alkyleneoxyalkylene having 2 to 12 carbon atoms or alkyleneiminoalkylene with 2 to 12 carbon atoms, in which the nitrogen atom contains hydrogen or alkyl with 1 to 6 carbon atoms as third substituent, y 1 or zero, X is oxygen or -NR, wherein R is hydrogen, lower alkyl having 1 to 6 carbon atoms or hydroxyalkyl having 1 to 6 carbon atoms, or X together with Q forms a piperazine ring, and Q is a nitrogenous group with the formulas (la) - (R2) k-N ^ \ r4 wherein n is 1 to 5; Q is also a cyclic amino group of the formulas 25th R3 © / TJS (lb) - (R2) k-N-t- ^ R and (2a) (2 B) (3 c) G® a ring-condensed aromatic amino group of the formulas Za Zb (4a) -IR2) k ~ V V (4b) - <R2). Za © V V © u and R " Za (4c) \ '9'V © G@ wherein Z is halogen or methyl and (a + b) is an integer from 0-3; or a heterocyclic amino group of the formula (5a) - (R2) k-E (5b) - (R2) k-E®-R5 A0 (5c) - (R2) k-E®-Ge is, where k is one or zero and E is N-hydroxyalkyl- or N-aminoalkyl-substituted pyrrolyl, pyrazolyl, imidazolyl, triazolyl, indolyl or indazolyl or py-ridazinyl, ring-substituted by hydroxyalkyl and aminoalkyl, pyrimidinyl, pyrazinyl or quinoxalinyl, (B) 0.1 to 5% by weight of an anionic fluorinated ten-side, (C) 0.1 to 25% by weight of an ionogenic fluorine-free ten-side, (D) 0.1 to 40% by weight of a non-ionic fluorine-free surfactant, (E) 0 to 70% by weight of a non-aqueous solvent and (F) contain enough water to fill the rest up to 100%. 3rd 628 247 4. Concentrates according to claim 3, characterized in that they (A) N- [3- (dimethylamino) propyl] -2 or -3- (l, l, 2,2-tetrahydroperfluoroalkylthio) succinamic acid, 40 (B) a perfluoroalkanoic acid or its potassium salt, (C) a partial sodium salt of N-lauryl-ß-iminodipropionic acid, (D) octylphenoxypolyethoxyethanol and (E) contain l-butoxyethoxy-2-propanol 45 5. Concentrates according to claim 3, characterized in that they (A) N- [3- (dimethylam & io) propyl] -2- or -3- (l, l, 3,3-tetrahydroperfluoroalkylthio) succinamic acid, (B) a perfluoroalkanoic acid or its potassium salt, so (C) a partial sodium salt of N-lauryl-ß-iminodipropionic acid and cocosimidazolinium ethosulfate, (D) octylphenoxypolyethoxyethanol and (E) 1-Butoxy ethoxy-2-propanoI contain. 6. Aqueous, film-forming concentrates in aerosol form for fire extinguishing or fire prevention by suppressing the Evaporation of flammable liquids, characterized in that they contain the water-diluted compositions according to claim 1 and an inert blowing agent. 7. A method of extinguishing or preventing fire, characterized in that 60 concentrates according to claim 1 are used after dilution with water. RfQmZ corresponds to