CA1065327A - Fluorinated compounds - Google Patents

Abstract

Abstract of the Disclosure The invention is directed to fluorinated compounds of the formula

Description

S3~

The below described invention deals with novel perfluoroalkyl group containing surfactants.
The importance of the surfactants resides in the fact that they act as wetting, emulsifying, solu-bilizing and/or dispersing agents. Although sur-factants have been prepared from many classes of compounds, more recently surfactants containing perfluoro alkyl (Rf) groups have been reported. Rf-substituted surfactants are especially valuable because they are known to reduce the surface tension of liquids more than any other surfactant. For instance, in water, surface tension of less than 17 dynes/cm can be obtained with fluorinated surfactants, whereas the non-fluorinated hydrocarbon analogs reduce the surface tension of water only to about 30 dynes/cm. For this reason the fluorinated surfactants have found application in such diverse areas as emulsion-polymerizations, self-polishing floor waxes, electro-plating, corrosion inhibitors, pains, and fire fighting compositions.

A variety of fluorinated, amphoteric and cationic surfactants have been disclosed in U.S. Patent 2,764,602, 3,555,089 and 3,681,413 and in German Offenlegungschrift

2,120,868; 2,127,232; 2,165,057 and 2,315,326. Although the compounds of the present invention also contain Rf groups, they are substantially different from the surfactants disclosed in the above listed patents.

10~;5;~;~7 Possible intermediates which can be used in preparing the surfactants of this invention are dis-closed in U.S. 3,471,518 wherein the addition of Rf-alkylenethiols to maleic acid and maleates is dis-closed and U.S. 3,706,787 wherein the addition pro-ducts of Rf-thiols to dialkyl maleates and monoalkyl maleates are disclosed. German Offenlegungsschrift 2,219,642 discloses Rf-alkylenethiol addition products with dialkyl amino-alkyl acrylates and methacrylates, which compounds are cationic surfactants and do not possess a 1,2-dicarboxylic moiety. While all fluori-nated amphoteric surfactants of the prior art are synthesized by quaternization of an appropriate ter-tiary amine with an alkylating agent, such as lactones, sultones or halogenated acids, the amphoteric sur-factants of this invention are prepared by a simple ring-opening reaction without the use of potentially carcinogenic alkylating agents. The surfactants of this invention are superior wetting agents, especially when used in combination with other fluorinated and nonfluorinated surfactants. Furthermore, they can be manufactured much more economically and safely.

10653Z~
The present invention is directed to novel fluorinated compounds which are preferably amphoteric or cationic and possess good surface active properties, and a process for their manufacture. The fluorinated compounds can be represented by the formulae Rf-Rl-S-(CH2)y~CH - COOH

and its isomer Rf-R -S-(CH2)y~CIH - COX - Q
CH2- COOH II and ,~0 Rf-R -S-(CH2)y~~CH - C -~ Q III
CH2--C~
wherein Rf is straight or branched chain perfluoroalkyl of 1 to 18 carbon atoms or said perfluoroalkyl substituted by perfluoroalkoxy of 2 to 6 carbon atoms, R is branched or straight chain alkylene of 1 to 12 carbon atoms, alkylenethioalkylene of 2 to 12 carbon atoms, alkyleneoxyalkylene of 2 to 12 carbon atoms or alkyleneiminoalkylene of 2 to 12 carbon atoms where the nitrogen atom contains as a third substituent, hydrogen or alkyl of 1 to 6 carbon atoms, y is 1 or zero, X i8 oxygen or -NR, wherein R is hydrogen, lower alkyl of 1 to 6 carbon atoms, hydroxyaIkyl of 1 to 6 carbon atoms, or X together with Q forms a piperazine ring, and Q is a nitrogen containing group selected from (1) an aliphatic amino group selected from (la) / R3 -(R )k-~

_ ~ _ (lb) -(R2)k-NR5 A ~
\ R4 and (lc) -(R )k-N - G

wherein R is a 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. Preferably R2 is a straight chain or branched alkylene of 2 to 5 carbon atoms;
k is 1 or zero, with the proviso, that if X is oxygen, k is 1, R3 and R4 are independently of each other hydrogen, alkyl group, substituted alkyl group of 1 to 20 carbon atoms, phenyl group, a alkyl or halogen substituted phenyl group of 6 to 20 carbon atoms, polyethoxy or polypropoxy group of 2 to 20 alkoxy units with the proviso that if X is oxygen, R3 and R are not hydrogen. The alkyl substituents can be aIkyl of 1 to 5 carbon atoms, dienyl, hydroxyl, carboxyl, halogen, alkylene-dialkylphosphonate such as methylene-diethylphosphonate or a group ~ R4 Phenyl subætituents can be methyl, halogen or hydroxyl. Preferably R3 and R are aIkyl groups of 1 to 4 carbons.
A ~ is any anion which forms an ammonium salt of the formula Anion A ~ is derived from aIkyl halideff, benzene or chlorobenzene sulfonate esters of alkyl alcohols and methyl and ethyl sulfates. A ~ is preferably Cl ~ , Br ~ , CH3CH20S03 Q or CH30S03 ~ .

R5 is hydrogen, an alkyl group or hydroxyalkyl group, aralkyl or groups of the formula -(CH2)n-C00-alkyl, said alkyl group having 1 to 18 carbons. Preferably, R5 is methyl, ethyl, propyl, butyl or benzyl.

G ~ is a group selected from the groups -(CH2)n-C00 ~ ; -(CH2)3S03 ~ ;

-CH-C00 ~ and -C-C00 1X2_COOH CH-COOH
where n is 1 to 5;
(2) cyclic amino groups selected from (2a) (2b) -R2-N ~ A ~ and (2C) -R2_N Y
G ~
wherein Y is a diradical group of the formulae:
-(CH2)4--(CH2)5--(CH2)2-0-(CH2)2 -(CH2)-CH-N-(CH2) -17l8 wherein R , R5, A ~ and G ~ are as defined above, R7 and R are independently hydrogen, a lower alkyl or hydroxy-lower alkyl group of 1 to 6 carbon atoms, With the proviso~ that if X is oxygen, R cannot be hydrogen.

(3) aromatic amino groUps selected from (3a) Za -(R )k ~0653'X7 (3b) /Za -(R )k ~ A
N

15 and (3c) Za -(R )k IN~
G ~

(4) fused-ring aromatic amino group selected from (4a) Za Zb -(R )k ~

(4b) Za Zb -(R )k ~ A
I

R5 and (4c) Za Zb ~R2 )k wherein Z is halogen or methyl, a + b is an integer from 0-3; and

(5) a heterocyclic amino group o~ the formula (5a) -(R2)k-E
(5b) -(R2)k-E ~ -R5 A

iO653~7 (5c) -(R2)k-E ~ -G
where k is one or æero and E is selected from N-hydroxyalkyl or N-aminoalkyl, substituted pyrrole, pyrazole, imidazole, triazole, indole or indazole, hydroxyaIkyl and aminoalkyl ring-substituted pyridazine, pyrimidino, pyrazino or quin-oxalino.
The present invention is further directed to aqueous film forming concentrate compositions for extinguishing or preventing fires by suppressing the vaporization of flammable liquids and to a process for fighting (extin-guishing or preventing) fires uherein these compositions are used.
The compounds represented above by formulae I and II where Q is ofstructures (la), (2a), (3a), (4a) or (5a) exist in solution in the form of their inner salts, having the general structures Rf-R -S-(CH2)y~fH~ COO Ia CH2 - COX-QH and Rf-R ~S(CH2)y~fH - COX-OH IIa CH2-COO ~) and thus are amphoteric surfactants.
The compounds of structure III are obtained through imidization of compounds of structures I and II, when X is -NH- by heating, either in bulk or in solution, to a temperature range of from 50 to 150C or preferably to a temperature of about 100 C. The compounds of this invention uhere Q is of structures (la), (2a), (3a~, (4a) or (5a) are prepared from mPleic or itaconlc anhydrides, perfluoroalkyl group-containing thiols and a polyamine or an aminoalcohol. Typically, they are prepared in two steps: first, maleic anhydride or itaconic anhydride is reacted uith an equimolQr amount of either an alcohol containing at least one tertiary amino group, or a primary or secondary amine containing at least one more primQry, secondary or tertiary amino group, to form an unsaturated intermediate half ester or half amide of structures:

/coo 9 HC or HC
COX-QH

H2C=CH-COO ~) where x is defined as above and Q is of structures (la), (2a), (3a), (4a) or (5a).
Compounds of this structure are described in the literature as comonomers for vinyl polymerization. For instance, 8H-COO ~
CH-CNX(CH2)3~(CH3)2 N-(3-dimethylaminopropyl)maleic acid amide, in United States 2,821,521.
For compounds in which X is -N-CH3 or -N-C2H5 and Q is -CH2CH2-N(CH3)2 the intermediate undergoes cyclization and forms a compound of structure:

\~/
N ~ CH2COO

~ - o I

CH3 (or -C2H5) These compounds are new and their structures have been confirmed by ~MR and by the absence of an acidic hydrogen.
Instead of preparing the intermediate from the anhydride by ring opening, other synthesis routes can be used; as for instance, transesterifica-tion or transamidification of a lower alkyl maleic, fumaric or itaconic half ester.
Synthesis of the novel surfactants is completed in a second reaction 10653;~7 step during which the perfluoroalkyl substituted thiol is added to the double bond of the intermediate by base catalysis. This reaction normally proceeds at room temperature, except where an intermediate of the above described cyclic type is formed; in this case addition of the thiol occurs only at temperatures of 85 C and above.
Alternately, the synthetic route can be reversed and the Rf-thiol added to the unsaturated, cyclic anhydride or its lower aIkyl monoester through base-catalysis or by a free-radical mechanism. The intermediate is then reacted with an alcohol containing at least one tertiary amino group or a primary or secondary amine containing at least one more primary, secondary or tertiary amino group which yields the desired product. The first synthesis route is preferred because of the high yield and purity of the product.
The mono-esters can be easily synthesized by reacting an equimolar amount of an unsaturated cyclic anhydride and the amino alcohol, either in bulk or in solution. The mono-amides can be prepared by reacting at a tem-perature below 50 C in a solvent equimolar amounts of an unsaturated cyclic anhydride with a polyamine. The useful solvents are such as methyl-ethyl ketone, diethylene glycol dimethylether, dimethylformamide, tetrahydrofuran, perchloroethylene, l,l,l-trichloroethane, dichloromethane, dioxane, dimethyl-sulfoxide, ~-methyl pyrrolidone. The amides can also be prepared in water or a mixture of water and an above listed solvent by adding the anhydride to the aqueous solution of the amine as described in greater detail in Canadian Patent 828,195.
The Rf-substituted thiol addition to the mono-esters and mono-amides i9 carried out in solution or in bulk at a temperature between 20 to 100 C. Useful solvents are alcohols such as methanol, ethanol, n-propanol, isopropanol, n- and isobutanol, amyl alcohol, n-hexanol, cyclohexane, benzyl alcohol and the like; ethers such as dimethyl ether, methyl ethyl ether, diethyl ether, di-n-propyl ether, diisopropyl ether, methyl n-butyl ether, ethyl n-butyl ether, ethylene glycol dimethyl ether, divinyl ether, diallyl ether, tetrahydrofuran and the like; ketones such as acetone, methyl ethyl ketone, methyl n-propyl ketone, diethyl ketone, hexanone-2, hexancne-3, _ 10_ methyl t-butyl ketone, di-n-propyl ketone, diisopropyl ketone, diisobutyl ketone, chloroacetone, diacetyl, acetyl acetone, mesityl oxide, cyclohexanone and t.1e like; N-methyl pyrrolidone, dimethylformamide, acetonitrile, benzene, chlorob-nzene, chloroform, methylenechloride, carbontetrachloride, dioxane, nitrobenzene, toluene and the like. Water can also be employed or a mixture of water and any one of the preceding solvents.
Preferred are solvent mixtures containing methanol, eth~nol, iso-propanol, carbitol or butylcarbitol, or water. If for a subsequent reaction, for instance quaternization with propanesultone, the alcohol has to be re-moved, a mixture of N-methylpyrrolidone and a low boiling alcohol such as methanol is preferred. Since the maleic mono-esters or maleic mono-amides already contain an amino group, no additional amine has to be added to catalyze the thiol addition.
The novel surfactants thus obtained are directly soluble in water or water/co-solvent mixtures. The solutions are essentially neutral. In dilute aqueous solution the tert-aminoalkyl mono-esters and mono-amides form polymeric aggregates leading to very high viscosities; these gel-type solu-tions are easily broken up by addition of a co-solvent, such as butylcarbitol, or a nonionic co-surfactant, such as an ethoxylated alkyl-phenol.
The compounds of this invention where Q is of structures (lb and c), (2b and c), (3b and c), (4b and c) and (5b and c) are prepared by quaterniza-tion of the amphoteric surfactants prepared as described above.
The quaternization reaction can be carried out in the presence or absence of an inert solvent. Suitable solvents are diethyl ether, aceton-itrile, dimethylformamide, N-methylpyrrolidone and the like.
The temperature of the reaction is not critical and may range from 0C to about 150 C depending on the reactivity of the quaternizing agent.
The resultant quaternary ammonium co~pounds are frequently obtained as solids when an inert solvent is employed. They can be readily separated, washed and dried. The products can be isolated from solution by addition of a nonsolvent, as will be kno~n to one skilled in the art. The products can be further purified if desired by recrystallization from an appropriate sol-~0653;~7 vent or solvent mixture. Produets obtained as viseous liquids can be further purified by extraction with a suitable solvent.
If the amino aleohol is a diol or a polyamine whieh contains at least three am-no groups at least two of whieh are primary or seeondary amino groups, it ean be reacted with two moles of maleic or itaconic anhydride and two moles of Rf-alkylenethiol yielding bis-R~-alkylenethiosuccinic acid half-amides, half-esters and suecinimides whieh ean be represented by the formulae r f ( 2)y 1 1 L CH2COX~T

and its isomer or ~Rf-R -S- ( CH2 )y~ I -C~

l H2C-C~

wherein T is a nitrogen eontaining divalent group seleeted from (1) R2 N /
(R2)_ (2) -R2-N N ~-R2-(3) -Rl9 ~ N

where R is an aliphatie hydro-earbon triradieal of 3 to 10 earbon atoms, preferably of 3 to 5 earbons. An example of strueture (3) is the 3-pyridyl-pentane 1,5-diradieal.
If in struetures I and II X is oxygen, Q is derived from tert-amino group eontaining aleohols of the formula (1) / R3 \ R4 iO653;~7 where R3 and R4 are as defined above.
Illustrative examples of the above represented alcohols are H0-CH2-CX2-N(CH3)2 2 2 (C2H5)2 2 3 ( 3)2 HO-(CH2)3-N(C2H5)2 H0-(CH2)3-N(c3 7)2 HO-(CH2)4-N(cH3)2 HO-(CH2)5-~(CH3)2 H-(CH2)6-N(CH3)2 ( 2)8 ( 3)2 HO(CH2)10-N(CH3)2 HO(CH2)12-N(CH3)2 H0-CH-fH2N(CH3)2 Ho-(cH2cH2o)xcH2cH2-N-(cH2) (CH2 2 Y
where x ~ y = 3-25 and z = 1-20 HO-CH2CH2-N(phenyl)CH2CH20H
H0-CH2CH2-N(tolyl) CH2CH20H
Ho-fH-cH2-N(phenyl)cH2fH-oH

/ ~OC2H5 CH2-P=O

Another class of tert-amino containing alcohols are cyclic compounds of the formula (2) HO_R

where R and Y are as defined above.
~ 13 ~

10653'~7 Illustrative examples of the above represented alcohols are 2)2 HO(CH2)2 N 3 HO(CH2)2 N ~ O

HO(CH2)3-- H ~-~CH2)3 Still other classes of tert-amino group containing alcohols are of the formulae (3) ~a Ho-R2_~3 N or t4) Zb Za HO-R

or (5) HO(R )k-E
wherein R , Z, E, a, b and k are as defined above.
Illustrative examples of such alcohols are 2-, 3- and 4-(2'-hydroxyethyl)pyridine 3-methyl-4-(2'-hyaroxyethyl)pyridine 2-methyl-4-(2'-hydroxyethyl)pyridine 2-, 3-, 4-, 5-, 6-, 7-, and 8-(2'-hydroxyethyl)quinolines 3-pyridyl-1,5-pentane diol.
When in formulae I or II X is -~R, such a moiety can be derived from a primary or secondary a~ine containing at least one other amino group.
Such amines can be represented by the formula (1) / R3 HN-(R )k-N
\ R

where R to R and k are as defined above.
Illustrative examples of the above represented amines are NH2(CH2)2N(cx3)2 NH2(CH2)2~(c4H9)2 CH3NH(CH2)2N(CH3)2 Ii~H2(CH2)3N(c3H7)2 NH2(CH2)4N(c2H5)2 NH2(CH2)5N(C2H3)2 NH2(CH2)ôN(c3H7)2 NH2(CH2)2N(C2H5)2 NH2(CH2)3N(CH3)2 CH3NH(CH2)2N(C2H3)2 NH2(CH2)3N(c4H9)2 CH3NH(cH2)4N(cH3)2 NH2(C~2)6~(C2H5)2 NH2(CH2)8~(c4H9)2 2( 2)2 (C3 7)2 NH3(CH2)3N(c2H5)2 C2H5NH(CH2)2N(c2H5)2 H2( H2)4 (CH3)2 NH2(CH2)5N(cH3)2 NH2(CH2)6N(C3H7)2 NH2(CH2)10N(C3H7)2 NH2(CH2)l2N(c3H7)2 CH3NH(CH2)3N(CH3)2 H2N(CH2)2N(CH2CH20H)2 ~ 15 -i H2N-N(CH3)2 CX3NH-N(CH3)2 H2I~CH2CH2CH2NH2 H2NCH2CH2N~2 H2NcH2cH2cH2N(cH3)cH2cH2cH2NH2 H2NcH2cH2NHcH2cH2oH .
Another class of primary and secondary amines containing at least one other amino group are heterocyclic compounds of the formulae (2) HN-(R2)-M ~ y or R

~ 5 HN H N-R

wherein R, R , R5 and Y are as defined above.
Illustrative examples of the amines above are N-(2'-aminoethyl)piperidine N-(2'-aminoethyl)morpholine N-(4'-aminobutyl)piperidine N-(2'-aminoethyl)-pyrrolidine N-methyl piperazine piperazine N-(2-hydroxyethyl)piperazine.
Still other classes of primary and ~econdary amines containing at least one other amino group are aromatic heterocyclic compounds containing five and six membered ringæ. These classes include _ 16 _ ~f)653Z7 (3) (4) Za Zb Za H-l-(CH2)V ~ H~

and (5)H2N(R )k-E
wherein R, R2, Z, E, a and b are as defined above, and v is an integer of from 0 to 12.
Illustrative examples of the amines represented above are 2-aminomethylpyridine 2-(2'-aminoethyl)pyridine 3-(2'-aminoethyl)pyridine 3-aminomethylpyridine 2,6-dichloro-3-aminomethylpyridine 2-methyl-3-(2'-Qminoethyl)pyridine 3-(4'-aminobutyl)pyridine 4-~minomethylpyridine 4-(2'-aminoethyl)pyridine 2-aminopyridine 3, 4, 5 or 6-methyl-2-aminopyridines 3, 4, 5 or 6-chloro-2-aminopyridines 203-aminopyridine 2-chloro-6-methyl-3-aminopyridine 4-aminopyridine dichloro-4-aminopyridines 2-aminopyrimidine 2-, 3-, 4-, 5-, 6-, 7- and 8-(4'-amino-butyl)quinolines 2-, 3-, 4-, 5-, 6-, 7- and 8-(3'-methy~minopropyl)quinolines 2, 3, 4, 5, 6, 7 or 8-aminoquinolines chloroaminoquinolines methylaminoquinolines guanine adenine.
Compounds having structures I, II or III, where Q is of structure (lb), (2b), (3b) or (4b) are derived from the corresponding amines by quaternization with compounds of the structure where R5 and A are as defined above.
Suitable compounds of the fo~mula R5A are those in which R5 is an alkyl group of 1 to 18 carbon atoms and A is any anion which forms an ammonium salt of the formula ~H4+A having a solubility in water of at least about 1%. Useful examples of R5A are the methyl-, ethyl-, propyl-, iso-propyl-, butyl-, isobutyl-, sec-butyl-, hexyl-, octyl-, ethylhexyl-, decyl-, dodecyl-, tetradecyl-, hexadecyl-octadecyl-chlorides, bromides and iodides;
benzylchloride; halo-alkanoic acid esters, and halo alkyl-alkyl ethers.
The normal alkyl halides, i.e., n-propyl, n-butyl, n-octyl or r,-hexadecyl, are preferred. Also useful are the toluene, benzene and chloro-benzene sulfonate esters of methyl, ethyl, propyl, butyl and like alcohols, and methyl and ethyl sulfate. When methyl or ethyl sulfate (R2S04) is used, the anion A in the product of the present invention will usually be a mixture of RS04- and ~04 ~fRS(CH2)yCHCOOH
L CH2COX-Q _¦ ~

Also useful are mineral acids, such as HCl, HBr, HI, H3P04 and H2S04, and organic acids, such as acetic, formic, acrylic acids.
The compounds of structures I, II and III where Q is of structure (lc), (2c), (3c), (4c) or (5c) are similarly derived from the corresponding amines by quaternization with (a) Hal-R6-COOH

wherein Hal stands for chlorine, bromine or iodine, ~ 18 ~

iO65327 R6 is an alkylene group of 1 to 5 carbon atoms, or a group -CH- -C-CH2COOH CH-COOH , (b) R O-CHCH2CO or o ~-lactones ( c ) CIH2CH2-S02 propane sultone wherein R is hydrogen or an aIkyl group of 1 to 6 carbon atoms.
The perfluoroalkyl thiols employed in the preparation of the com-poundæ of this invention are well kno~n in the prior art. For example, thiols of the formula RfRl-SH have been described in a number Or United States patents including 2,ô94,ggl; 2,961,470; 2,965,677; 3,088,849; 3,172,190;
3,544,663 and 3,655,732.
Thus, IJnited States Patent 3,655,732 discloses mercaptans of for-mula Rf-R -SH
where R is alkylene of 1 to 16 carbon atoms and Rf is perfluoroalkyl and teaches that halides of formula Rf-R -hal are well known; reaction of RfI with ethylene under free-radical conditions gives Rf(CH2CH2)aI while reaction of RfCH2I with ethylene gives RfCH2(CH2CH2)aI as is further taught in United States Patents 3,o88,849; 3,145,222; 2,965,659 and 2,972,638.
United States Patent 3,655,732 ~urther discloses compounds of for-mula R~-R'-X-R"-SH
where R' and R" are alkylene of 1 to 16 carbon atoms, with the sum Or the carbon atoms of R' and R" being no greater than 25; Rf is perfluoroalkyl of 4 through 14 carbon atoms and X is -S- or -NR "'- where R " ' is hydrogen or ~0~53,f~7 alkyl of 1 through 4 carbon atoms.
United States Patent 3,544,663 teaches that the mercaptan RfCH2CH2SH
where Rf iB perfluoroalkyl of 5 to 13 carbon atoms, can be prepared by reacting the perfluoroaIkyl alkylene iodide with thiourea or by adding H2S
to a perfluoroalkyl substituted ethylene (Rf-CH=CH2), which in turn can be prepared by dehydrohalogenation of the halide Rf-CH2CH2-hal.
The reaction of the iodide Rf-R -I with thiourea followed by hydrolysis to obtain the mercaptan Rf-R -SH is the preferred synthetic route.
The reaction is applicable to both linear and branched chain iodides. Many useful per n uoroalkoxyalkyl iodides are described in United States Patent 3,514,437 of general formula (CF3)2CF0 CF2CF2(CH2CH2)m where m is 1-3.
Particularly preferred herein are the thiols of formula RfCH2CH2SH
where Rf is perfluoroalkyl of 6 to 12 carbon atoms. These Rf-thiols can be prepared from RfCH2CH2I and thiourea in very high yield.
Illustrative examples of preferred perfluoroalkylalkylenethiols are CloF21CH2CH2SH

\ CF0(CF2CF2)l to 3 CH2CH2 Especially preferred perfluoroalkylalkylenethiols are 10653Z~
t CloF21CH2CH2SH
and mixtures thereof.
Unsaturated dicarboxylic cyclic anhydrides which can be employed in preparing the surfactants of this invention can be amleic and a~kyl and halogen substituted maleic ~nhydrides such as citraconic and chloro and dichloromaleic anhydrides. Preferred are itaconic and maleic and most pre-ferred maleic anhydride.
The compounds of this invention, as noted above, are effective surfact~nts and therefore can be employed in all applications where surfactants are required. These surfactants would be employed as prior art surfactants which is self evident to those skilled in the art. Specific examples where the instant surfactant can be employed are as wetting agents in coatings, waxes, emulsions, paints. They are especially useful when for-mulated with other nonfluorinated surfactants as fire fighting agents. A
particular advantage of these surfactants is their low toxicity to aquatic life.
A particular advantage of the compounds of this invention where Q
is represented by structures (la), (2a), (3a), (4a) and (5a) is that they are amphoteric surfactants made without a specific quaternization reaction step which require the use of carcinogenic alkylating agents such as ~-lactones and propane sultones. The prior art amphoteric surfactants require such quaternization step. The compounds of this invention are particularly useful in the preparation of aqueous fire fighting formulations, especially when used in combination with non-fluorinated surfactants. Such formulations have superior hydrocarbon fire fighting properties.
Preferred surfactants of this invention are the amphoteric surfactants of formulae Ia and IIa where Q is of structures (la), (2a) or (3a). More preferred are those where Rf is linear perfluoroalkyl of 6 to 12 carbon atoms, R is ethylene and y is zero. The most preferred surfactants are those where X is ~R and Q is of structure (la) where R is a straight _ 21 _ chain alkylene of 2 to 5 carbon atoms, R is hydrogen, methyl or ethyl and R3 and R4 are methyl or ethyl.
It is also well-known that synergistic surface tension effects are achieved from mixtures of different types of Rf-surfactants, as for instance nonionic and anionic Rf-surfactants, alone or in combination with classical hydrocarbon co-surfactants as told by ~ernett and Zisman (J. Phys. Chem. 65, 448, (1961) ) .
Tuve et al in United States 3,258,423 also disclose the use of aqueous solutions of certain Rf-surfactants or Rf-surfactant mixtures alone or in combination with solvents and other additives as efficient fire fight-ing agents. Based on the Tuve et al findings many other fire fighting agents containing different Rf-surfactant systems have been disclosed as shown in United States 3,315,326 and 3,772,195.
Fire fighting agents containing Rf-surfactants act in two ways:
a. As foams, they are used as primary fire extinguishing agents.
b. As vapor sealants, they prevent the re-ignition of fuels and solvents.
It is this second property which makes fluorochemical fire fighting agents far superior to any other known fire fighting agent.
These Rf-surfactant fire fighting agents are commonly known as AFFF
(standing for Aqueous Film Forming Foams~. AFFF agents act the way they do because the Rf-surfactants reduce the surface tension of aqueous solutions to such a degree that the solutions will wet and spread upon non-polar and water immiscible solvents even though such solvents are lighter than water;
they form a fuel or solvent vapor barrier which will rapidly extinguish flames and prevent re-ignition and reflash. The criterion necessary to attain spontaneous spreading of two immiscible phases has been taught by Harkins et al, J. Am. Chem. 44, 2665 (1922). The measure of the tendency for spontaneous spreading is defined by the spreading coefficient (SC) as follows:
sc = ya - yb - yi where SC = spreading coefficient ya - surface tension of the lower liquid phase 10653Z~7 yb = surface tension of the upper aqueous phase yi = interfacial tension between the aqueous upper phase and lower liquid phase.
If the SC i8 positive, the surfactant solution should spread and film forma-tion should occur. The greater the SC, the greater the spreading tende~cy.
This requires the lowest possible aqueous surface tension and lo~est inter-facial tension, as is achieved with mixtures of certain Rf-surfactant(s) and classical hydrocarbon surfactant mixtures.
Commercial AFFF agents are primarily used today in so-called 6% and 3% proportioning systems. ~% means that 6 parts of an AFFF agent and 9~
parts of water (fresh, sea, or brackish water) are mixed or proportioned and applied by conventional foam making equipment wherever needed. Similarly an AFFF agent for 3% proportioning is mixed in such a way that 3 parts of this agent and 9~ parts of water are mixed and applied.
Today AFFF agents are used wherever the danger of fuel solvent fires exist and especially where expensive equipment has to be protected.
They can be applied in many ways, generally using conventional portable handline foam nozzles, but also by other techniques such as with oscillating turret foam nozzles, subsurface in~ection equipment (petroleum tank farms), fixed non-aspirating sprinkler systems (chemical process areas, refineries,), underwing and overhead hangar deluge systems, inline proportioning systems (induction metering devices), or aerosol type dispensing units as might be used in a home or vehicle. AFFF agents are recommended fire suppressants for Class A fires such as fires of wood, cloth, paper, rubber or plastics or Class B fires, such as fires of flammable solvents, gasoline, gases or greases particularly the latter. Properly used alone or in con~unction with dry chemical extinguishing agents (twin-systems) they generate a vapor-blanketing foam with remarkable securing action.
AFFF agents generally have set a new standard in the fighting of fuel fires and surpass by far any performance of the previously used protein foams. However, the performance of today's commercial AFFF agents is not the ultimate as desired by the industry. The very high cost of AFFF agents is limiting a wider use and it is, therefore, mandatory that more efficientAFFF agents which require less fluorochemicals to achieve the same effect are developed. Furthermore, it is essential that secondary properties of presently available AFFF agents be improved. The new AFFF agents should have: a) a lower degree of toxicity (fish toxicity is a very essential element whenever AFFF agents are dispensed in large quantities and when there is a chance that such agents might pollute receiving streams and lakes; this is a ma~or problem on test grounds where AFFF agents are often used); b) a lower chemical oxygen demand (COD); good biodegradability (so as not to hin-der the activity of microorganisms in biological treatment systems); c) aless corrosive character so that they can be used in light weight containers made of aluminum rather than heavy, non-corrosive alloys; d) improved long term storage stability; e) good compatibility properties with conventional dry chemical extinguishers; f) an improved vapor sealing characteristic and seal speed, and most importantly; g) have such a high efficiency that instead of using 3 and 6% proportioning systems it might become possible to use AFFF
agents in 1% or lower proportioning systems. This means that 1 part of an AFTF agent can be blended or diluted with 99 parts of water. Such highly efficient concentrates are of importance because storage requirements of AFFF
agents will be greatly reduced, or in the case where storage facilities exist~
the capacity of available fire protection agent will be greatly ~ncreased.
AFFF agents for 1% proportioning systems are of great importance therefore wherever storage capacity is limited such as on offshore oil drilling rigs, offshore atomic power stations, city fire trucks and so on. The performance expected from an AFFF agent today is in most countries regulated (for example United States Navy Military Specification MIL-F-24385 and its subsequent amendments).
The novel AFFF agents described of this invention are in comparison with today's AFFF agents superior not only with regard to the primary per-formance characteristics such as control time, extinguishing time and burn-back resistance but additionally, because of their ~ery high efficiency offer the possibility of being used in 1% proportioning systems. Furthermore, they offer desirable secondary properties from the standpoint of ecology as wellas economy.
As indicated above the present invention is further directed to aqueous film forming concentrate compositions for extinguishing or preventing fires by suppressing the vaporization of flammable liquids, said composition comprising A) 0.5 to 25% by weight of a fluorinated compound (surfactant), of any of the formulae I to III, B) 0.1 to 5% by weight of anionic fluorinated surfactant, C) 0.1 to 25% by weight of ionic non-fluorochemical surfactant.
D) 0.1 to 40% by weight of nonionic non-fluorochemical surfactant, E) 0 to 70g by weight of solvents, and F) water in the amount to make up the balance of 100%.
To form effective compositions, a mixture of various surfactants must attain surface tensions of less than about 26 dynes/cm. Each component (A) to (E) may consist of a specific compound or a mixture of compounds.
The above composition is a concentrate which, as noted above, uhen diluted with water, forms a very effective fire fighting formulation by form-ing a foam which deposits a tough film over the surface of the flammable li~uid which prevents its further vaporization and this extinguishes the fire.
It i8 a preferred fire extinguishing agent for flammable solvent fires, particularly for hydrocarbons and polar solvents of low water solu-bility, in particular for:
Hydrocarbon Fuels - such as gasoline, heptane, toluene, hexane, Avgas*, VMP
naphtha, cyclohexane, turpentine, and benzene;
_olar Solvents of Low Water Solubility - such as butyl acetate, methyl iso-butyl ketone, butanol, ethyl acetate, and Polar Solvents of High Water Solubility - such as methanol, acetone, iso-propanol, methyl ethyl ketone, ethyl cellosolve and the like.
It may be used concomitantly or successively with flame suppressingdry chemical powders such as sodium or potassium bicarbonate, ammonium *Trademark - 25 -10~53Z7 dihydrogen phosphate, C02 gas under pressure, or Purple K, as in so-called Twin-agent systems. A dry chemical to AFFF agent ratio would be from 4,5 to 13,6 kg of dry chemical to 7,5 to 37,853 1 AFFF agent in use concentration (i.e. after 0.5%, 1%, 3%, 6% or 12% proportioning). In a typical example 9 kg of a dry chemical and 18,9 1 of AFFT agent could be used. The com-position of this invention could also be used in con3unction with hydrolyzed protein or fluoroprotein foams.
The foams of the instant invention do not disintegrate or otherwise adversely react with a dry powder such as Purple-K Powder ~P-K-P). Purple-K
Powder is a term used to designate a potassium bicarbonate fire extinguishing agent which is free-flowing and easily sprayed as a pouder cloud on flammable liquid and other fires.
The concentrate is normally diluted with water by using a propor-tioning system such as, for example, a 3% or 6~ proportioning system whereby 3 parts or 6 parts of the concentrate is admixed with 97 or 94 parts respec-tively of water. This highly diluted aqueous composition is then used to extinguish and secure the fire.
Component (B) is a fluorinated anionic surfactant. The exact structure of these surfactants is not critical and they may be chosen from compositions wherein the fluoroaliphatic surfactant is a water soluble fluoroaliphatic compound represented by the formula RfQmZ
wherein Rf is a fluorinated saturated monovalent non-aromatic radical con-taining from 3 to 20 carbon atoms in which the carbon atoms of the chain are substituted only by fluorine, chlorine or hydrogen atoms with no more than one hydrogen or chlorine atom for every two carbon atoms, and in which a divalent oxygen or tri~alent nitrogen atom, bonded only to carbon atoms, can be present in the skeletal chain;
~ , where m is an integer of 0 or 1, is a multivalent linking group comprising alkylene, sulfonamido alkylene and carbonamido alkylene radicals;
and Z is a water solubilizing polar group comprising anionic radicals.

Preferred anionic groups are -C02 and -S03 . The anionic surfactant should contain 30-65% of carbon bound fluorine in oraer to attain suitable solubility properties. The anionic surfactant may be present as free acid, an aIkali metal salt thereof, = onium, or substituted ammonium.
Illustrative exa~ples of Rf-anionics which can be used in the com-positions of this invention are the below shown acids and their alkali metal salts. The patent numbers appearing in parenthesis are patents which more fl~lly disclose the represented class of compounds.
Carboxylic Acids and Salts thereof RfCOOH (Scholberg et al, J. Phys. Chem, 57, 923-5(1953) ft 2)1-20 (Ger. 1,916,669) RfO(CF2)2 20COOH (Ger. 2,132,164) RfO(CF2)2_20(cH2)2-2o (Ger. 2,132,164) RfO(CH2)1 20COOH (U.S. 3,409,647) RfS02N(C2H5)CH2COOH (U.S. 3,258,423) RfO(CF20)3CF2COOH (Fr. 1,531,902) RfO (CF2CIFO\ CF2COOH (Fr. 1,537,922) \ CF3/3 RfO[CF(CF3)CF20]CF(CF3)CON(CH3)CH2COOH
(U.S. 3,798,265) (C2F5)2(CF3)CCE2COOH (Brit. 1,176,4g3) CloFlgOC6H4CON(CH3)CH2COOH (Brit. 1,270,662) Rf(CH2)1 3SCH(COOH)CH2COOH ~U.S. 3,706,787) Rf(CH2)1 12s(cH2)l 17COOH Ger. 2,239,709; U.S. 3,172,900 Sulfonic Acids and Salts Thereof RfS03H (U.S. 3,475,333) RfC6H4S03H (Ger. 2,134,973) f( 2)1-20 3 (Ger. 2,309,365) f 2 H 2C6 4 03 (Ger. 2,315,326) RfS02N(cH3)(c2H40)l-2o 3 (S.A. 693,583) RfCH2CH20CH2CH2CH2S03H (Can. 842,252) RfOC6H4S03H (Ger 2;230,366) 106532'7 C12F230C6H4S03H (Ger. 2,240,263) (C2F5)3CO(CH2)3S03H (Brit. 1,153,854) CF3(C2F5)2CO(CH2)3S03H (Brit. 1,153,854) (c2F5)2(cF3)ccH=c(cF3)so3H (Brit. 1,206,596) RfOCF(CF3)CF20CF(CF3)CONHCH2S03H (U.S. 3,798,265) PhosphQnates, Phoæphates, Related Phosphoro Derivatives, and Salts Thereof RfPO(OH)2 (Rf)2PO(OH) (Ger. 2,110,767) PfS2N(Et)C2H4PO(OH)2 (Ger. 2,125,836) RfCH20PO(OH)2 (Ger. 2,158,661) C8F150c6H4cH2Po(OH)2 (Ger. 2,215,387) RfOC6H4CH2PO(OH)2 (Ger. 2,230,366) Others (and Salts Thereof) RfS02N(CH3)C2~40S03H (Ger. 1,621,107) RfC6H40H (U.S. 3,475,333~

Rf(CH2)1_20S23Na (Ger. 2,115,139) f( 2)1~20so2N(cH3)cH2cH2s2o3~a (Ger. 2,115,139) RfS02H (U.S. 3,562,156) In the sulfonate class of the fluorinated anionic surfactant~ a particularly preferred type of compounds are sulfonates formed by the reac-tion of 1,3-propane sultone and a perfluoroalkylthiol and have the structure Rf-R -S- ( CH2 ) 3S03 ~) Z ~
wherein Rf and Z are aæ defined above and R is as defined below.
The perfluoroaIkyl thiols employed in the preparation of the sultones are well known in the prior art. For example, thiols of the formula RfR -SH have been described in a number of United States patents including 2,894,991; 2,961,470; 2,965,677; 3,o88,849; 3,172,190; 3,544,663 and 3,655,732.
Thus, United States Patent 3,655, 732 discloses mercaptans of for-mula R~_Rl_SH
where _ 28 _ lQ653Z7 Rl is alkylene of 1 to 16 carbon atoLs and Rf is perfluoroalkyl and teaches that halides of formula Rf-R -hal are well known; reaction of RfI with ethylene under free-radical conditions gives Rf(CH2CH2)aI while reaction of RfCH2I with ethylene gives RfCH2(CH2CH2)aI as is further taught in United States Patents 3,o88,849; 3,145,222; 2,965,659 and 2,972,638.
United States Patent 3,655,732 further discloses compounds of for-mula Rf-Rl-x-R~-sH
where R and R" are alkylene of 1 to 16 carbon atoms, with the sum of the carbon atoms of Rl and R" being no greater than 25; Rf is perfluoroalkyl of 4 through 14 carbon atoms and X is -S- or -~R " '- where R " ' is hydrogen or alkyl of 1 through 4 carbon atoms.
The reaction of the iodide Rf-Rl-I with thiourea followed by hydrolysis to obtain the mercaptan Rf-R -SH i6 the preferred synthetic route.
The reaction is applicable to both linear and branched chain iodides. Many uæeful perfluoroalkoxyalkyl iodides are described in United States Patent 3 514 487, of general formula:
(CF3)2CF0 CF2CF2(CH2CH2) I
where m is 1-3.
Particularly preferred herein are the thiols of formula:
RfCH2CH2SH
where Rf is perfluoroalkyl of 6 to 12 carbon atoms. These Rf-thiols can be prepared from RfCH2CH2I and thiourea in very high yield.
Component (C), an ionic non-fluorochemical water soluble surfactant is chosen from the anionic, cationic or amphoteric surfactants as represented in the tabulations contained in Rosen et al, Systematic Analysis of Surface-Active A~ents, Wiley-Interscience, New York, (2nd edition, 1972), pp. 485-544, which is incorporated herein by reference.
It iB particularly convenient to use amphoteric or anionic fluorine-free surfactants because they are relatively insensitive to the effects of fluoroaliphatic surfactant structure or to the ionic concentration of the aqueous solution and furthermore, are available in a wide range of relative solubilities, making easy the selection of appropriate materials.
Preferred ionic non-fluorochemical surfactants are chosen with primary regard to their exhibiting an interfacial tension below 5 dynes/cm at concentrations of .01-3% by weight. They should also exhibit high foam expansions at their use concentration, be thermally stable at practically useful application and storage temperatures, be acid and alkali resistant, be readily biodegradable and non-toxic, especially to aquatic life, be readily dispersible in water, be unaffected by hard water or sea water, be compatible with anionic or cationic systems, form protective coatings on materials of construction, be tolerant of pH, and be available commercially and inexpen-sive.
In accordance with the classification scheme contained in Schwartz et al, Surface Active Agents, Wiley-Interscience, N.Y., 1963, anionic and cationic surfactants are described primarily according to the nature of the solubilizing or hydrophilic group and secondarily according to the way in which the hydrophilic and hydrophobic groups are ~oined, i.e. directly or indirectly, and if indirectly according to the nature of the linkage.
Amphoteric surfactants are described as a distinct chemical cate-gory containing both anionic and cationic groups and exhibiting special behavior dependent on their isoelectric pH range, and their degree of charge separation.
Typical anionic surfactants include carboxylic acids, sulfuric esters, alkane sulfonic acids, alkylaromatic sulfonic acids, and compounds with other anionic hydrophilic functions, e.g., phosphates and phosphonic acids, thiosulfates, sulfinic acids, etc.
Preferred are carboxylic or sulfonic acids since they are hydrolytically stable and generally available. Illustrative examples of the anionic surfactants are CllH230(C2H40)3 5S03Na 10653'~7 Disodium salt of alkyldiphenyl ether disulfonate Disodium salt of sulfosuc-cinic acid half ester derived alcohol 10-12 ethoxylated Sodium Alpha olefin sulfonates CllH23CONH(CH3)C2H4S03Na CllH23coN(cH3)cH2co2Na Typical cationic classes include amine salts, quaternary ammonium compounds, other nitrogenous bases, and non-nitrogenous bases, e.g.
phosphonium sulfonium, sulfoxonium, also the special case of amine oxides which may be considered cationic under acidic conditions.
Preferred are amine salts, quaternary ammonium compounds, and other nitrogenous bases on the basis of stability and general availability.
Non-halide containing cationics are preferred from the standpoint of cor-rosion. Illustrative examples of the cationic surfactants are bis(2-hydroxyethyl)tallowamine oxide dimethyl hydrogenated tallowamine oxide isostearylimidazolinium ethosulfate cocoylimidazolinium ethosulfate lauroylimidazolinium ethosulfate [ 12H250cH2lcHcH2T(cH2cH2oH2]cH3so4 t3 [ 11 23CONH(CH2)3N(CH3)3] CH3S04 ~
[ 17 35CONH(CH2)3N(CH3)2CH2CH20H] + N03 -The amphoteric non-fluorochemical surfactants include compounds which contain in the same molecule the follo~ing groups: amino and carboxy, amino and sulfuric ester, amino and alkane sulfonic acid, amino and aromatic sulfonic acid, miscellaneous combinations of basic and acidic groups, and the special case of aminimides.
Preferred non-fluorochemical amphoterics are those which contain 106S3Z'7 amino and carboxy or sulfo groups, and the Pminimides.
The aminimide surfactants have been described in Chemical Reviews Vol. 73, No. 3 (1973). Generally, they are the carboxaminimides of the general formulae:

/ Rl R5 R(H) -C-N-N - R2 or R(H)n-C-N-N \ C~IR4-C - OH

and sulfonylaminimides of the general formulae:

Rl R1 R5 R(H)nS02N-N - R2 or aminocyanoimides, aminonitroimides, or functionally substituted aminimides as described in United States 3,499,032, United States 3,485,806 and British 1,181,218.
Of the above-mentioned aminimides, the carboxaminimides are most preferred because of the combination of very desirable surface active prop-erties listed below:
a) they are highly surface active and possess very low inter-facial tensions at low concentrations and hence afford films of exceedingly high-spreading coefficient;
b) they are amphoteric and thus compatible with all types of fluorosurfactants - anionic, cationic, nonionic, or amphoteric;

c) they are thermally stable at practically useful application 0 and storage temperatures;
d) they are acid and aIkali stable;
e) they are biodegradable and non-toxic;
f) they are readily dispersible in water;
g) they are high-foaming and only moderately affected by water hardness;
h) they are inexpensive and commprcially available.

Illustrative examples of the non-fluorochemical amphoteric ~0653'~7 surfactants are:
coco fatty betaine (C02 ) cocoylamidoethyl hydroxyethyl carboxymethyl glycine betaine cocoylamidoammonium sulfonic acid betaine cetyl betain (C-type) a sulfonic acid betaine derivatiYe C~3 CllH23CONNCHOHCH3 CH
~ ~3 C13H27COl CH2CHHC 3 CH+3 Cl5H3lcoN~(cH3)2cH2cHoHcH3 C17H35CNN(CH3)2CH2CHHCH3 _+

_+
C15H31CONN(CH3)3 N ~ 2 ~ CH

ll I / 2 2 CH2C2 ~CH2C02Na A coco-derivative of the above Coco Betaine C12 14H25_29NH2CH2CH2 (triethanolammonium salt) 5~ \
CH2CH2C2Na A nonionic non-fluorochemical surfactant component (D) is incor-porated in the aqueous fire compositions primarily as a stabili~er and sol-ubilizer for the compositions, particularly uhen they are diluted uith hard water or sea water. The nonionics are chosen primarily on the basis of their hydrolytic and chemical stability, solubilization and emulsification char-acteristics (e.g. measured by XLB-hydrophilic-lipophilic balance), cloud point in high salt concentrations, toxicity, and biodegradation behavior.
Secondarily, they are chosen with regard to foam expansion, foam viscosity, foam drainage, surface tension, interfacial tension and wetting character-istics.
Typical classes of nonionic surfactants useful in this invention include polyoxyethylene derivatives of alkylphenols, linear or branched alcoholæ, fatty acids, mercaptans, alkylamines, alkylamides, acetylenic glycols, phosphorus compounds, glucosides, fats and oils. Other nonionics are amine oxides, phosphine oxides and nonionics derived from block polymers containing polyoxyethylene and/or polyoxypropylene units.
Preferred are polyoxyethylene derivatives of alkylphenosl, linear or branched alcohols, glucosides and block polymers of polyoxyethylene and polyoxypropylene, the first two mentioned being most preferred.
Illustrative examples of the non-ionic non- n uorochemical surfactants are Octylphenol(EO)9 10 " (EO)16 " (EO)30 Nonylphenol (EO)g 10 (E)12 13 Lauryl ether (EO)23 Stearyl ether (EO)lo Sorbitan nolaurate (EO)20 Dodecylmercaptan (EO)lo Block copolymer of (EO)x(PO)4 CllH23cONtc2H~oH)2 ~ 3~ ~

10653~7 C12H25N(CH3)20 ~( CH2CH20 )xH
C12H25~ ~
(CH2CH20) H
x + y = 25 NOTE: EO and PO used above mean ethylene and propylene oxide repeating unit, respectively.
Component (E) is a solvent which acts as an antifreeze, a foam stabilizer or as a refractive index modifier so that proportioning systems can be field calibrated. Actually, this i8 not a necessary component in the composition of this invention since very effective AFFF concentrates can be obtained in the absence of a solvent. In fact, this is one of the unexpected and unusual features of this invention since prior art compositions as a rule must employ a relatively high percentage of a solvent. However, even with the compositions of this invention it is often advantageous to employ a sol-vent especially if the AFFT concentrate will be stored in subfreezing tem-peratures. Useful solvents are disclosed in United States patents 3,457,172; 3,422,011 and 3,579,446, and German patent 2,137,711.
Typical solvents are alcohols or ethers such as:
ethylene glycol monoalkyl ethers, diethylene glycol monoalkyl ethers, propylene glycol monoalkyl ethers, dipropylene glycol monoalkyl ethers, triethylene glycol monoalkyl ethers, l-butoxyethoxy-2-propanol, glycerine, diethyl carbitol, hexylene glycol, butanol, t-butanol, isobutanol, ethylene glycol and other low molecular weight alcohols such as ethanol or isopropanol wherein the alkyl groups contain 1-6 carbon atoms.
Preferred solvents are l-butoxyethoxy-2-propanol, diethyleneglycol monobutyl ether, or hexylene glycol.
Still other components which may be present in the formulation are:
--Buffers whose nature is essentially non-restricted and which are exem-plified by Sorensen's phosphate or McIlvaine's citrate buffers.
--Corrosion inhibitors whose nature is non-restricted so long as they are compatible with the other formulation ingredients.
--Chelating agents whose nature is non-restricted, and which are exemplified by polyaminopolycarboxylic acids, ethylenediaminetetraacetic acid, citric acid, gluconic acid, tartaric acid, nitrilotriacetic acid, hydroxyethyl-ethylenediaminetriacetic acid and salts thereof.
--High molecular weight foam stabilizers such as polyethyleneglycol, hydroxypropyl cellulose, or polyvinylpyrrolidone.
The concentrates of this invention are effective fire fighting compositions at any pH level, but generally such concentrates are ad~usted to a pH of 6 to 9, and more preferably to a pH of 7 to ô.5, with a dilute acid or alkali. For such purpose may be employed organic or mineral acids such as acetic acid, oxalic acid, sulfuric acid, phosphoric acid and the like or metal hydroxides or amines such as sodium or potassium hydroxides, triethanolamine, tetramethylammonium hydroxide and the like.
As mentioned above, the compositions of this invention are con-centrates which must be diluted with water before they are employed as fire fighting agents. Although at the present time the most practical, and there-fore preferred, concentrations of said composition in water are 3% and 6~because of the availability Or fire fighting equipment which can automatically admix the concentrate with water in such proportions, there is no reason why the concentrate could not be employed in lower concentrations of from 0.5%
to 3% or in higher concentrations of from 6% to 12%. It is simply a matter of convenience, the nature of fire and the desired effectiveness in extin-guishing the flames.
An aqueous AFFF concentrate composition which would be very useful in a 6% proportioning system comprises A) 1.0 to 3.5g by weight of amphoteric fluorinated surfactant, B) 0.1 to 2.5% by weight of anionic fluorinated surfactant, C) 0.1 to 4.0% by weight of ionic nonfluorochemical surfactant, D) 0.1 to ô.0% by weight of a nonionic non-fluorochemical surfactant, - 36 _ 10653;~7 E) 0 to 20% by weight of solvent and water in the amount to make up the balance of 100%.
The subject composition can be also readily dispersed from an aerosol-type container by employing a conventional inert propellant such as Freon* 11, 12, 22 or ~2' ~2 or air. Expansion volumes as high as 50 based on the ratio of air to liquid are attainable.
The most important elements in this new AFFF system are the amphoteric Rf-surfactants of component (A).
These amphoteric Rf-surfactants reduce surface tensions of the aqueous solutions to about 20 dynes/cm ana act as solubilizers for the Type B Rf-surfactants contributing to most of the excellent characteristics of the novel AFFF agents of this invention. The anionic Rf-surfactants of component (B) act as surface tension depressants for the amphoteric surfactant of com-ponent (A) (synergistic Rf-surfactant mixtures) depressing the surface tension to 15-16 dynes/cm and are usually present in a much lower concentration than the Rf-surfactants of component (A). Rf-surfactants of component (B) further-more increase the spreading speed of aqueous AFFF films on hydrocarbon fuels and contribute significantly to the excellent resealing capacity of the novel AFFF agent. The ionic or amphoteric hydrocarbon surfactants of component (C) have a dual function. They act as interfacial tension depressants by reduc-ing the interfacial tension of the aqueous Rf-surfactant solution containing components (A) and (B) Rf-surfactants, from interfacial tensions as high as 10 dynes/cm to interfacial tensions as low as .1 dyne/cm. Furthermore, the cosurfactantf of component (C) act as foaming agents and by varying the amount and proportions of component (C) cosurfactants, it is possible to vary the foam expansion of the novel AFFF agent. The nonionic hydrocarbon surfactants of component (D) in the novel AFFF agent have also a multiple function by acting as solubilizing agents for the Rf-surfactants of components (A) and (B) having poor solubility characteristics. They furthermore act as stabiliz-ing agents, especially of AFFF agent sea water premixes and also influence the AFFF agent foam stability and foam drainage time as expalined later.
Furthermore they influence the viscosity of A~ agents which is very *Trademark - 37 -10~53Z7 critical especially in the case of 1% proportioning systems. Solvents of com-ponent (E) are used similarly as solubilizing agents for Rf-surfactants, but also act as foam stabilizers, to serve as refractive index modifiers for field calibration of proportioning, to reduce the viscosity of highly con-centrated AFFF agents, and as anti-freezes. Whereas commercial 6% propor-tioning AFFF agents have high solvent contents of greater than 20%, this invention teaches the preparation of comparable formulations with excellent performance at solvent contents as low as 3%.
Some of the solvents present in the formulated AFFF agents are only present because they are carried into the product from the ~f-surfactant synthesis. Besides the contribution the ingredients so far listed may have on the performance of the novel AFFF agent, it must also be mentioned that these candidates were also selected because they have very low toxicity as shown in the experimental part of this application. As mentioned before other additives in the novel AFFF agent might be advantageous such as:
Corrosion inhibitors (for instance in the case where aqueous AFFF premixes are stored for several years in uncoated aluminum cans).
Chelating agents (if premixes of AFFF aeents and very hard water are stored for longer periods of time).
~uffer systems (if a certain pH level has to be maintained for a long period of time).
Anti-freezes (if AFFF agents are to be stored and used at sub-freezing tem-peratures).
Polymeric thickenin~ agents (if higher viscosities of AFFF agent -- water premixes are desired because of certain proportioning system requirements), and so on. Today's commercial AFFF agents are only capable of use on 6 and 3% proportioning systems. The composition of the instant AFFF agents and the ranges of the amounts of the different active ingredients in these novel AFF
aeents will be expressed for 0.5 to 12% proportioning systems. If the con-centration in a composition for 6% proportioning is doubled then such a con-centrate can be used for a 3% proportioning system. Similarly if the con-centration of such a 6% proportioning system is increased by a factor of 6 _ 38 _ then it can be used as a 1% proportioning system. As comparative data in the experimental part will show it is possible to make such 1% proportioning systems primarily:
A. Because of the higher efficiency of the novel Rf-surfactants used and the smaller amounts therefore needed.
B. Because of the rather low amounts of solvents required in the new AFFF agents to achieve foam expansion ratios as specified by the military.
In the examples, references are made to specifications used by the induætry and primarily the military and to proprietary tests to evaluate the efficiency of the claimed compositions. More specifically, the examples refer to the following specifications:
Surface Tension and Interfacial Tension - ASTM D-1331-56 Freezing Point - ASTM D-1177-65 pH - ASTM D-1172 Sealability Test Ob,~ective: To measure the ability of a fluorochemical AFFF formula-tion (at the end use concentration) to form a film across, and seal a cyclo-hexane surface.
Procedure: Ten mls of cyclohexane is pipetted into a 40 mm evap-20 orating dish in the evaporometer cell. Helium flowing at 1000 cc per minuteflushes the cyclohexane vapors from the cell through a 3 cm IR gas cell mounted on a PE 257 infrared spectrophotometer (a recording infrared spectro-~hotometer with time drive capability). The IR absorbence of the gas stream in the region of 2050 cm is continuously monitored as solutions of formula-tions are infused onto the surface. Formulations are infused onto the cyclo-hexane surface at a rate of 0.17 ml per minute using a syringe pump driven lcc tuberculin syringe fitted with a 13 cm 22 gauge needle, whose needle is ~ust touching the cyclohexane surface.
Once the absorbence for 'tunsealed" cyclohexane is established, the 30 syringe pump is started. Time zero is when the very first drop of formula-tion solution hits the surface. The time to 50% seal, percent seal at 30 seconds and 2 minutes are recorded. Time to 50~ seal relates well to film 10653'~7 speed (see below) percent seal in 30 seconds and 2 minutes relate well to the efficiency and effectiveness of the film as a vapor barrier.
Film S~eed Test ObJective: To determine the speed with which an AFFF film spreads across a cyclohexane surface.
Procedure: Fill a 6 cm a~uminum dish one-half full with cyclo-hexane. Fill a 50 ~1 syringe with a 6% solution of the test solution. In~ect 50 ~1 of the solution as rapidly and carefully as possible down the wall of the dish such that the solution flows gently onto the cyclohexane surface.
Cover the dish with an inverted Petri dish. Start the timer at the end of the inJection. Observe the film spreading across the surface and stop the timer the moment the film completely covers the surface and record the time.
Match Test Ob~ective: To determine roughly the sealing ability of an AFFF
fil~.
Procedure: Fill an aluminum weighing dish (58 x 15 mm) two-thirds full with reagent cyclohexane. Carefully pour about 2 ml of test AFFF solution over the surface. Strike a wooden match, and after the initial flare-up of the match has subsided, immerse the flame quickly through the sealed surface and then retract it from the dish. The flame will be snuffed out. Repeat with additional matches until sustained ignition is achieved and note the number of matches used.
Fire Tests The most critical test of the subJect compositions is actual fire tests. The detailed procedures for such tests on 2.60 sq.m., 4.647 sq.m. and 117.0 sq.m. fires are set forth in the United States Navy Specification MIL,F-24385 and its Amendments.
Procedure: Premixes of the compositions of this invention are pre-pared from 0.5 to 12% proportioning concentrates with tap or sea water, or the AFFF agent is proportioned by means of an in-line proportioning system.
The test formulation in any event is applied at an appropriate use concentra-tion.

~ 40 The efficacy of the compositions o~ the present invention to extin-guish hydrocarbon fires was proven repeatedly and reproducibly on 2.60 sq. m.
gasoline fires as well as on 117.0 sq. m. fires conducted on a 12.19 m in diameter circular pad. The tests were frequently conducted under severe environmental conditions with wind speeds up to 16 km per hour and under prevailing su~mer temperatures to 35C. The fire performance tests and sub-sidiary tests -- (foamability, film formation, sealability), film speed, vis-cosity, drainage time, spreading coefficient, and stability, all confirmed that the compositions of this invention performed better than prior art AFFF
compositions.
The most important criteria in determining the effectiveness of a fire fighting composition are:
1. Control Time - The time to brin8 the fire under control or secure it aM er a fire fighting agent has been applied.
2. Extinguishing Time - The time from the initial application to the point when the fire is completely extinguished.
3. Burn-Back Time - The time from the point when the flame has been completely extinguished to the time when the hydrocarbon liquid reignites when the surface i9 sub~ected to an open flame.
4. Summation of % Fire Extinguished - When 4.645 or 117.05 sq. m.
~ires are extinguished the total of the "percent of fire extinguished" value are recorded at 10, 20, 30 and 40 second intervals. Present specification for 4.645 sq. m. require the "Summation" to fires be 225 or greater, for 117.05 sq. m. fires 205 or greater.
2.60 sq. m. Fire Test This test was conducted in a level circular pan 1.83 m in diameter -(2.60 square meters), fabricated from 0.635 cm thick steel and having sides 12.70 cm high, resulting in a freeboard of approximately 6.35 cm during tests.
The pan was without leaks so as to contain gasoline on a substrate of water.
The water depth was held to a minimum, and used only to ensure complete cov-erage of the pan with fuel. The nozæle used for applying agent had a flow rate of 7.57 1 per minute at 7.03 kg/sq. cm pressure. The outlet was mod-10653'~7 ified by a "wine tip" spreader having a 3.175 mm wide circu'ar arc orifice 4.76 cm long.
The premix solution in fresh water or sea water was at 21C - 5.5 C.
The extinguishing agent consisted of a 6-percent proportioning concentrate or its equivalent in fresh water or sea water and the fuel charge was 37.85 1 of gasoline. The complete fuel charge was dumped into the diked area within a 60-second time period and the fuel was ignited within 60 seconds after com-pletion of fheling and permitted to burn freely for 15 seconds before the application of the extinguishing agent. The fire was extinguished as rapidly as possible by maintaining the nozzle 1.07 to 1.22 m above the eround and angled upward at a distance that permitted the closest edge of the foam pat-tern to fall on the nearest edge of the fire. When the fire was extinguished, the time-for-extinction was recorded continuing distribution of the agent over the test area until exactly 11.36 1 of premix has been applied (90-second application time).
The burnback test was started with 30 second after the 90-second solution ~pplication. A weighted 30.48 cm diameter pan having 5.08 cm side walls and charged with o.946 1 of gasoline was placed in the center of the area. The fuel in the pan was ignited ~ust prior to placement. Burnback time commenced at the time of this placement and terminated when 25 percent of the fuel area (0.65 sq. meter), originally covered with foam was aflame. After the large test pan area sustained burning, the small pan was removed.
117.0 sa. m. Fire Test This test was conducted in a level circular area (117.0 sq. m.).
The water depth was the minimum required to ensure complete coverage of the diked area with fuel. The nozzle used for applying the agent was designed to discharge 189.27 1 per minute at 7.07 kg/sq.cm.
The solution in fresh water or sea water was at 20 C - 5.50C and contPined 6.o - 0.1 % of the composition of this invention. The fuel was 1135.6 1 of gasoline. No tests were conducted with wind speeds in excess of 16 km per hour. The complete fuel charge was dumped into the diked area as rapidly as possible. Before fueling for any test run, all extinguishing ~0653'~7 agent from the previous test run was remo~ed from the diked area.
The fuel was ignited within 2 minutes after completion of fueling, and was permitted to burn freely for 15 seconds before the application of the extinguishing agent.
The fire was extinguished as rapidly as possible by maintaining the nozzle 1.07 to 1.22 m above the ground and angled upward at a distance that permitted the closest edge of the foam pattern to fall on the nearest edge of the fire.
At least 85 percent of the fire was to be extinguished within 30 seconds, and the "percent of fire extinguished" values were recorded.
Example 1 N~3-(dimethylamino)propyl]-2 and 3-(1.1~2.2-tetrahydroperfluorodecylthio)succinamic acid C8F17CH2CH2SCHCOo ~) CH2coNH(cH2)3NH(cH3)2 and C8Fl7cH2cH2scHcoNH(cH2)3NH(cH3)2 CH2COO ~) Maleic anhydride (10.0 g; 0.102 mole) and a mixture of ethyleneglycol dimethyl ether (100 g) and N,N-dimethyl formamide (60 g) were placed in a stirred reaction flask kept under nitrogen atmosphere and cooled to 10C
in an ice bath. 3-dimethylaminopropylamine (10.4 g; 0.102 mole) was added drop-wise during one-half hour at a reaction temperature of 10-15 C. The resulting white suspension was stirred at room temperature for 1 hour.
A small amount of this product was dried, washed with heptane and dried in vacuo at 30C for 12 hours. Infrared analysis and NMR signals were characteristic for a compound of structure:

/coo ~
HC

HC \
CONH-(CH2 )3N(CH3)2 N-(3-dimethylaminopropyl) maleic acid amide.
~ 43 ~

1,1,2,2-tetrahydroperfluorodecyl mercaptan (4~.0 g; 0.102 mole) was added all at once. l`he resulting mixture was stirred for 64 hours at roo~ temperature.
The thick suspension was filtered and the solids washed with acetone then dried at room temperature under vacuum (0.1 mm Hg) for lô hours. The product was obtained as a white powder weighing 61.2 gms (yield = 88.2%) having a m.p. of 123-128 with slow decomposition (gas evolution) above the melt. The infrared spectrum was consistent with the structure in particular the amide band at 1650 cm in the solid phase and at 1660 cm 1 in dilute chloroform solution and the carboxylate asymmetrical and symmetrical stretching bands at 1550 cm and 1320 to 1390 cm 1 respectively. An ~MR spectrum was consistent with the structure and showed the ~ollowing signals:

2-68 ppm ~-CH3i 1.8-2.1 NCH2CH2CH2N

The surface tension (~ ) of the aqueous solution of the above named compound is 19.8 dynes/cm. The surface tension in this and the following examples was measured with a Du Nouy tensiometer at 0.1 % concentration in water at 25C.
Example 2 N-~3-(dimethvlamino)propyl~ -? and 3-(1.1~2~2-tetrahydroperfluoroalkylthio)succinamic acid RfCH2CH2SCHC ~
CH2CONH(CH2)3NH(CH3)2 and its isomer Maleic anhydride (100 g; 1.02 le) and N-methylpyrrolidone (400 g) were stirred in a reaction flask under an inert atmosphere and cooled to 0 C
in an ice-salt mixture. 3-Dimethylaminopropylamine (106 g; 1.04 mole) dis-solved in N-methylpyrrolidone (100 g) was added drop-wise during 40 minutes at 0-10 C. The dark tan suspension was stirred at room temperature for 20 minutes when methanol (800 g) was added and the resulting mobile suspension was heated to 45C. 1,1,2,2-Tetrahydroperfluoroalkyl mercaptan ~483 gi 0-94 mole) (a mixture of compounds having varying alkyl groups as follows: C6-25 C8-50%; and Clo-25%) was added during 10 minutes at 45-50C to give an amber solution which was stirred at 45C for 3 hours. The completenessof reaction was checked by the disappearance of perfluoroalkylethyl mercaptan to trace amounts of the reaction mixture, as detected by gas chromatography. Identity of the product was confirmed by infrared absorption for the a~ide function at 1655 cm 1 and the carboxylate ran at 1560 cm 1 and 1325-1400 cm 1. Gas chromatography showed three perfluoroalkyl acid areas, two solvent areas and trace areas due to the mercaptans. Proton NMR signals obtained were essen-tially identical to those for Example 1. The compound melted at 95 to 115 C.
~he surface tension of the aqueous solution of said compound was 17.7 dynes/
cm.
Following the procedure described abo~e, compounds analogous to Example 2 were prepared from maleic anhydride and the following indicated starting materials;

_ C~ ~o ~ ~ ~ o~
m ~ 2 ~ 2 ,, ~o N N

N N ~ ~ ~ W :1; V

I ~i CU I
I CU ~ t!~ I
O ~N I N C.) C.) N Z_ ~C N

~N

O N ~U N N N
~1 C~
~0 ~ ~0 Exam~le 8 N-met~yl-N-(2'-N',N'-dimethylaminoethyl)-2 and 3-~1 1,2,2-tetrahydroperfluoroalkylthio)suc-cinamic acid RfCH2CH2S-CHC ~ ~ / CH3 CH2C07-CH2CH2NH \ and isomer Rf is a mixture of C6F13 (25%), C8F17 (50%) and CloF21 (25%) Powdered maleic anhydride (0.033 moles, 3.24 g) was added in por-tions to a cooled solution of (N,N',N'-trimethyl)-ethylene-1,2-diamine (0.033 moles, 3.47 g) in 6.7 g water. The reaction was carried out under nitrogen and maintained at 10-20C with an ice bath. After the addition was complete the bath was removed and the reaction mixture was stirred at room temperature for 12 hours.
A small amount of the solution was dried in vacuo at 30 C for 12 hours. A dry, white powder was obtained whose NMR signals were charac-teristic for a compound of structure:

\~/

~H

CH3No acidic hydrogen could be titrated.
2-methyl-2,4-pentane diol (20.13 g) was added to the light yellow solution followed by perfluoroalkyl ethyl mercaptan (0.3135 moles, 14.65 g).
The resulting white suspension was heated to 90 C with stirring until the completion of the reaction (6.5 hours). The clear light yellow solution was cooled to room temperature and diluted to 30% solids with water (23 g). The turbid solution was clarified by filtration (5~ porosity asbestos pad) to yield 66.5 g (93.4%) of a clear light yellow solution. Infrared analysis was consistent with the structure. The surface tension ( ~s) of the aqueous iO653'X7 solution of the above compound was 18.3 dynes/cm.
Example 9 Following the above procedure, the compound N-ethyl-~-(2'-N'N-dimethylaminoethyl)-2 and 3 -(1,1~2,2-tetrahydroperfluoroalkylthio)succinamic acid was prepared from maleic anhydride, RfC2H4S~ and N,~-dimethyl-N'-ethyl-ethylene-1,2-diamine. The surface tension of this co~pound was 20.2 dynes/cm.
Example 10 N-(2-dimeth~laminoethvl)-2 and 3-(1~1~2~2-tetra-hydroperfluoroalkylthio)succinamic acid RfCH2CH2S-CHCOO ~) ¦ ~ / CH3 2C0 ~ CH2CH2 N H \ and isomer Powdered maleic anhydride (0.033 moles, 3.24 g) was added in por-tions to a cooled solution of (N,N-dimethyl)-ethylene-1,2-diamine (0.033 moles, 2.90 g) in 6.7 g water. The reaction was carried out under nitrogen and maintained at 10-20C with an ice bath. After the addition was complete the bath was removed and the reaction mixture was stirred at room temperature overnight, 2-methyl-2,4-pentane diol (20.13 g) was added to the light yellow solution followed by perfluoroalkyl ethyl mercaptan (0.3135 moles, 14.65 g).
The resulting white suspension was heated with stirring at 30C to completion (6.5 hours). The light yellow solution was cooled to room temperature and diluted to 30% solids with water. It was clarified by filtration through a 5 ~ porosity asbestos pad to yield 66.5 g (93.4%) of a clear light yellow solution. The surface tension of the aqueous solution of the above compound was 22.0 dynes/cm.
Following the procedure described above, compounds analogous to Example 10 were prepared from maleic anhydride and the starting materials as shown below:

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.

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.

Example 22 2 and 3~ 2~2-tetrah~droperfluorodecylthio) succinic acid-mono-[2-(N,N-dimethyl)aminoethyl~
ester C8F17CH2cH2scHcoo ~ / CH3 CH2COOCH2CH2NH \ and isomer A solution of maleic anhydride (o.o408 moles, 4.00 g) in acetone (15 g) was added to N,N-dimethyl aminoethanol (o.o408 moles, 3.64 g) in acetone (10 g) at 10 C. The product precipitated as an acetone insoluble resin. After 30 minutes methanol (20 g) was added and a dispersion was formed. 1,1,2,2-tetrahydroperfluorodecyl mercaptan (.o408 moles, 19.6 g) was added and as the reaction proceeded, a clear solution was formed.
The reaction was allowed to stand at room temperature for 24 hours. VPC
and TLC showed no unreacted mercaptan. The yellow solution was dried under vacuum to a light yellow wax. The Yield was 26.5 g (98.5%).
The surface tension ( ~s) of the aqueous solution of the above named compound is 16.3 dynes/cm.
Following the procedure described above, compounds analogous to Example 22 were prepared from maleic anhydride and the starting materials shown below:

-52 _ a) o ~ ~ ~ ~ N
r~ 1 ~', ~ N N
U~

.

}~' . , ' X
~ ~ , 8 o N ~ T ~ ~ ~

O ~ ~ N
z _ N ~DN b~N X ~ N
' U ~ U ~
., , , ~, ~ .

- 1 ¦ U ~ U ~N ~N N

p; C~ U tA~ ~ C) U

G) ~;

. ' '' ...... . . ., ~ ,_, , . _ _.,,, .. ,.. .. _ . ._ .. . . . .

Example 29 2 and 3-(1,1,2~2-tetrahydro~erfluorodecylthio) succinic acid mono-(2'-quinolino ethyl) ester CôFl7cH2cH2s-lcHcoo ~ and isomer CH2COOCH2CH2~

A solution of maleic anhydride (0.0255 moles, 2.5 g) in dichloromethane (10 g) was added dropwise to a stirred solution of 2-(2-hydroxyethyl)-quinoline (0.0255 moles, 4.2 g) in dichloromethane (20 g). The mixture was cooled to 0C and kept at -10 C during the addition. A Mer the addition was completed the dry ice/acetone bath was removed and the reaction mix-ture was allowed to warm up slowly to 20 C. Then 1,1, 2,2-tetrahydroperfluorodecyl mercaptan (0.0255 moles, 12.24 g) were added. The brown solution was allowed to stand overnight at room temperature and then heated to 26 C for 2 hours. TLC and VPC showed no unreacted mercaptan. The solution was dried under vacuum to yield 18.2 g of a light brown powder (94.8~).
The surface tension t ~ s) of the aqueous solut~on of the above named compound is 22 dynes/cm.

_ ~4 -Example 30 N~N'-bis[(n-propyl-3)-2 and 3-(1~1~2~2-tetrahydro-perfluorooctylthio)succinamic monoamido3piPerazine C6F13CH2CH2s- lcH-coo ~ OOC-7H-S-CH2CH2C6Fl3 CH2CNHCH2CH2CH2N ~ NHCH2CH2CH2 11 2 and isomer 1,4-bis(3-aminopropyl)piperazine (0.0255 moles, 5.1 g) in 10 g acetone was added dropwise to a dry ice/isopropanol cooled solution of maleic anhydride (0.0510 ~oles, 5.0 g) at -10 to 0C. A
white precipitate came out immediately and the reaction mixture was stirred for one hour at 20 C.
1,1,2,2-tetrahydroperfluorooctyl mercaptan (0.0510 moles, 19.27 g) was added and the reaction was stirred for 3 days at room temperature until TLC showed no traces of unreacted mercaptan. The amber solution was dried under high vacuum to 29.1 of yellow powder (99% yield).
Infrared spectrum was consistent for the structure.
The surface tension ( ~s) of the aqueous solution of the above named compound is 22 dynes/cm.

~ 55 -10653Z'7 Example 31 N[3-(dimethylamino)propyl]-2 and 3-(heptafluoro-isopropoxy-1,1~2~2-tetrahydroperfluoroalkylthio) succinamic acid C~
~ (CF2)ncH2cH2s-cH-coo ~ ~ / CH3 CF3 C 2 HCH2CH2CH2NH \

and isomer Maleic anhydride (0.0255 moles, 2.5 g) was dissolved in 10 g acetone. 3-dimethylamino propyl~mine (0.0255 moles, 2.61 g) in 5 g acetone was added dropwise so that the reaction temperature was maintained at 5-10C.
As the reaction proceeded, an acetone insoluble resin was formed and after the amine addition was completed 10 g methanol was added to form a homogeneous mixture Heptafluoroisopropoxy-1,1,2,2-tetrahydro-perfluoroalkyl mercaptan (0.0255 moles, 14.60 g) was added and the reaction mixture was stirred for 2 days until TLC showed no traces of the mercaptan. The pale yellow solution was dried under vacuum to give 18.9 g of white powder (95.9% yield).
Infrared analysis was consistent for the above structure.

:10653Z'7 Example 32 N-[3-(dimethylamino)propyll-2 and 3-(1~1~2~2~
tetrahydroperfluorooctylthio) methylsuccinamic acid IH_COO ~
¦ ~ / CH3 2 HCH2 H2cH2NH \ and isomer 3-dimethylamino-propylamine (0.25 moles, 2.55 g) in 5 g acetone was added to a cooled solution of itaconic anhydride (.025 moles, 2.80 g) in 10 g acetone at 5-10C. There was an immediate exothermic reaction and the light brown product precipitated out slowly. 10 g methanol was added to dissolve the product and the reaction mixture was stirred for one hour.
1,1,2,2-tetrahydroper n uorooctyl mercaptan (.025 les, 9.45 g) was added and the reaction was stirred for 2 d~ys at room temperature. TLC showed no unreacted mercaptan. ~he clear amber solution was dried under vacuum to give 14.0 g of a yellow wax (94.6% yield).
Infrared analysis was consistent with the above structure.

10653'~7 Example 33 This example shows the preparation of sulfonates by quaternization with propane sultone.
41.7 e (0.061 moles) of the surfactant prepared in Example 1, was dissolved in an equal amount of acetone and 7.45 g (0.061 moles) of propane sultone was added, the reaction mixture was stirred at 50C for 8 hours; the IR spectrum showed a strong new band at 1035 cm 1, indicating formation of the sulfonate; a C=0 band at 1660 cm as well as bands at 1780 and 1710 cm 1, indicating that some imide had been formed. No carboxylate and no dimethylamino group was visible in thè IR spectrum which is generally consistent with the structure shown below. The product was a waxy solid which formed a strongly foaming aqueous solution.
H

8 17 H2C 2 S IC COOX ~ 3 CH2-CON-CH2CH2CH2- _CH2CH2CH2S3 H ¦~

and its isomer.

Elemental analysis: C N S F

Calculated: 33.6 3.4 7.6 39.6 Found: 33.1 3.58.0 38.7 The surface tensio~ s) of the aqueous solu-tion of the above named compound is 21.5 dynes/cm.

10653'~
On heating to 120 C for 30 minutes, itsIR spectrum changed. The band at 1660 cm 1 dis-appeared completely and the two imide bands at 1780 and 1720 cm grew very strong, no carboxylate and no dimethylamino absorption were present. This IR spectrum was consistent with the structure:

8 17 2 2 CH C ~ ~ H3 l ~-cH2cH2cH2-l CH2CH2CH2 3 The surface tension ( ~s) of the &queous solution of the above named compound is 22.5 dynes/cm.

10653'~7 Example 34 Example 33 was repeated with the Rf-sub-stituted succinamic acid of Example 16. The sulfonate (A) for~ed easily and was a waxy, brown solid. On heating imidization occurred to the compound of structure (B) COO~
C8Fl7cH2cH2-s-cH

2 ~ CH2CH2CH2S3 (A) VheQt ~P
C8Fl7cH2cH2-s-cH ~
I ~ - CH2 ~ 2 H2 H2 3 (B) H2C ~

The surface tension ( ~s) of the aqueous solu-tion of the above named compound is 19.1 dynes/cm.
IR analysis of (A) and (B) were consistent with the given structures.
Elemental analysis of (B) C ~ S F
Calculated: 33.4 3.4 7.7 38.8 Found: 34.6 3.3 8.1 37.2

-6~ _ Example 35 This example shows the formation of Rf-sub-stituted succinimide from the corresponding succinamic acid.
IR analysis of the compound made in Example 1 revealed a strong carboxylate band at 1600 cm and a strong C=0 band at 1660 cm consistent wlth structures:

C8F17-CH2CH2-s- I_COO ~3 CH2-co-l-cH2cH2cH2l(c~3)2 ~A) H H

C Fl7-cH2cH2-s-lc-co~H-cH2cH2cH2~(c 3)2 (A') When thiæ material was heated to 120C for 20 minutes, it foamed slightly; it became insoluble in water, but dissolved in acidic aqueous medium. Its IR analysis showed two strong bands at 1780 and 1710 cm characteristic for the cyclic imide with the bands at 1600 and 1660 cm reduced to weak shouldersj also present was a strong absorption at 2770 and 2820 cm 1 characteristic for the dimethyl amino group. The spectrum was consistent with the structure:

H
C8F17-CH2CH2-S-C C\ CH3 IH C ~ C 2CH2CH2 ~ ~ CH3 (B) _ 61 -~0653Z7 N-(~',N'-dimethyl-3-amino propyl)-2-(1,1,2,2-tetra-hydro heptadecylfluorothiodecyl) succinimide.

Elemental Analysis for (B):
C N S F
Calculated: 33.4 4.1 4.7 47.5 Found: 34.2 4.0 5.3 46.4 The following examples describe the preparation of additional quaternized derivatives.
Exam~le 36 2.04 g (0.003 mole) of [2 and 3-(1,1,2,2-tetra-hydroperfluorodecyl thio)]-~,N-dimethyl(3-aminopropyl) succinamic acid (of Example 1) were dissolved in 5cc 35% aqueous HCl. The clear solution was evaporated and the residue dried in vacuo (0.1 mm Hg) at 80C for 12 hours, to yield 2.1 g of a white powder, having the structure:

CH2-CO~H-CH2CH2CH2~(CH3)2H Cl and isomer The surface tension ( ~s) of the aqueous solution of the above named compound is 18.8 dynes/cm.

Example 37 2.04 g (0.003 mole) of 2 and 3-(1,1,2,2-tetrahydroperfluorodecylthio)-N,N-dimethyl amino-propyl succinamic acid melting at 123-128C was sealed in an ampoule with 0.43 g (O.OG3 mole) methyl iodide in 10 g isopropanol and heated for 3 hours.
The pale pink suspension was filtered and dried to yield 1.6 g of white powder melting at 205-250C
having the structure C8F17CH2CH2S-CH _ C ~ ~(CH ~ I
¦ NCH2CH2CH2N 3 3 CH2-C ~

The surface tension ~ ~s) of the aqueous solution of the above named compound is 24.9 dynes/cm.
Exam~le 38 2.04 g (0.003 mole) of 2 and 3-(1,1,2,2-tetra-hydroperfluorodecylthio)-N,N-dimethyl(3-aminopropyl) succinamic acid was refluxed with 0.38 g (0.003 mole) benzyl chloride in 10 g ~hanol until basic tertiary amine was no longer detected. The æolution was evaporated to yield 2.17 g of an off-white semi-solid having the structure ~0 C8Fl7cH
¦ NCH2CH2CH2N(CH3)2CH2 ~ Cl \\o iO653Z7 The surface tension ( ~s) of the aqueous solution of the above named compound is 20.8 dynes/cm.
Example 39 2.04 g (0.003 mole) of [2 and 3-(1,1,2,2-tetrahydroperfluorodecylthio)]-N,N-dimethyl(3-amino-propyl)succinamic acid was stirred with 0.28 g (0.003 mole) chloroacetic acid in 30 g water overnight. No free tertiary amine was detectable. 20 g methanol was added to break the foam and the clear solution was evaporated at 60 C and vacuum to give 2.1 g of off-white wax having the structure.

C8F17-CH2CH2Scx-c~ ~3 ¦ CH2CH2CH2N(CH3)2CH2C00 CH2-C~

The surface ter,sion ( ~s) of the aqueous solution of the above named compound is 17.4 dynes/cm.

- 6~ _ 10653'~7 Exam~le 40 2.04 g (0.003 mole) of [2 and 3-1,1,2,2-tetrahydroperfluorodecylthio]-N,N-dimethyl(3-amino propyl)succinamic acid was dissolved in 30 ml ether.
A solution of 0.22 g (0.0031 mole) ~-propiolactone in 5 ml ether was added dropwise over 5 minutes at 15C. The mixture was stirred for 2 hours at 30C
and the ether was removed in a rotary evaporator.
Yield: 2.2 g of a product having the structure:

H2 CONHCH2CH2CH2N(CH3)2CH2-CH2coo and isomer The surface tension ( ~s) of the aqueous solution of the above named compound is 22.6 dynes/cm.

10653'~7 C~J N CO
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s $ ~: ¢ ¢ ~c ~06S3'~7 _~ ^ ^ N

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10653A~7 Table 2 Anionic Fluorinated Surfactants* used in Examples 41 to 117 _. . _ . ... _ .Anionic . Formula - Actives -lOO~h or Rf-Surfactant Name as ~ioted .
Bl pel^fluoroalkanoic acid RfCO2H
B2 potassium perfluoroalkanoate 25% RfCO2K - 25% in lO hexylene glycol -l5% t-butyl alcGh~cl -~ ~later B3 2 ~-dihydroper~luoroalkanoic acid RfCH2C02H
B4 sodium l l 2 2-tetrahydroperflu- RfCH2CH2S (C~2)3s03~a oroalkylthio propanesulfonate . R~ = C6 C8 C10 B5 perfluoro-heptanoic acid75 25 Q C6Fl3C02H
B6 perfluoronon- .
anoic acid 4 87 9 C8FI7C02H
B7 perfluoro-undecanoic acid 0 11.5 88.5 CloF2lCO2H
B8 potassium perfluoroheptanoate C6Fl3CO2K - 25% as in B2 _ _ _ ~here Rf is typically a mixture of C6Fl3 (32%) C~Fl7 (~2~) and CloF2l (6%) and traces of other homologs ~o653'<:7 Table 3 Ionic (and Amphoteric) Surfactants used in Examples 41 to 117 . _ Type A-Anionic Ionic C-Cationic Surfactant AM-Amphoteric Name - % Actives as Noted or ~ 100%
Cl AM trimethylamine laurimide C2 AM partial sodium salt of N-lauryl ~-iminodipropionic acid (30%) C3 AM N-lauryl, myristyl ~-aminopropionic acid (50%) C4 C cocoimidazolinium ethosulfate C5 AM dimethyl(2-hydroxypropyl)amine laurimide C6 AM dimethyl(2-hydroxypropyl)amine myristimide C7 AM dimethyl(2-hydroxypropyl)amine palmitimide C8 AM trimethylamine myristimide C9 AM acylamidoammonium sulfonic acid betaine (50%) C10 AM dicarboxylic lauric derivative-imidazolinium amphoteric (38~) Cll A sodium salt of ethoxylated lauryl alcohol sulfate (27~) C12 AM disodium salt of N-lauryl ~-iminodipropionic acid - 6g -,ab1~ ~!
Nonionic Sur~actants used in Examp~es 41 to 117 Nonionic , Name Surfactant X Actives as Noted or -100~ . -~_ Dl octylphenoxypolyethoxyethano1 (12) 99~ -D2 polyoxyethylene (23) lauryl ether D3 octylphenoxypolyethoxyethanol (16) -70X

D4 octylphenoxypolyethoxyethanol (10) -99%

D5 octylphenoxvpo1yethoxyethanol (30) -70 D6 nonylphenoxypolyethoxyethanol (20) D7 - nonylphenoxypolyethoxyethanol (30) -70X

D8 branched alcohol ethoxylate (15) Numbers in brackets indicate ethylene oxide repeating units.

Table 5 Solvents used in Examples 41 to 117 Solvent Name ... _ . . .. . _ _ .
El l-butoxyethoxy-2-propanol E2 1-butoxy-2-propanol/2-methyl-2,4-pentanediol 2/3 ratio E3 diethylene glycol monobutyl ether E4 2-methy1-2,4-pentanediol -.
E5 . tetrahydrothiophene-l,l-dioxide E6 ethylene glycol .. .

Exam~les 41 to 44 AFFF agents having a composition as shown in Table 6 have identical compositions except that the Rf-group in the ampho-teric Rf-surfactant varies from a pureperfluorohexyl to a pure perfluorooctyl to a pure perfluorodecyl group, and to a mixture Or perfluorohexyl, perfluorooctyl and perfluorodecyl in a ratio of approximately 1:2:1.
As the surface tension data in Table 6 show, the lowest values are obtained with the pure C8 isomer followed by the amphoteric Rf-surfactant with mixed Rf-groups. On the other hand, lowest interfacial tension values are obtained with the C6 isomer and the Rf-isomer mixture. As a result the hiehest spreading coefficient of 6.5 dynes/cm is obtained with the Rf-mixture. Rf-mixture amphoteric fluorinated surfactants of mype A with mixed Rf-groups are, of course, from an economical standpoint, most desirable.
The pH-values of the compositions in these and the following examples are generally in the range of 7 to 8.5, unless otherwise mentioned.

10653'~7 Table 6 ~ffect of Amphoteric Rf-Surfactant (Component A) and its Homolog Content Example ~os. 41 to 44 Amphoteric Rf-Surfactant Solution Various: (as stated) Anionic Rf-Surfactant . . . . . . . . Bl: 0.29 %
Amphoteric Cosurfactant . . . . . . . C2: 8.33 % (30 % solids) ~ther Cosurfactant . . . . . . . . . C4: 0.83 %
~onionic Cosurfactant . . . . . . . . D2: 2.08 %
Solvent . . . . . . . . . . . . . . . El: 5.00 %
Water . . . . . . . . . . . . . . . . . . Balance Example ~o. 41 42 43 44 . .
Rf-surfactant A6, 30 % as is 4.93 Rf-surfactant A7, 30 % as is 4.93 Rf-surfactant A8, 100 % as is 1.48 Rf-surfactant Al, 30 % as is 4.93 Surface tension* dynes/cm 17.7 16.9 18.0 17.2 Interfacial tension* dynes/cm 9 1.7 1.7 0.9 Spreading coefficient* dynes/cm 6.o 6.0 4 9 6.5 * 3 percent dilution in distilled water; interfacial tension against cyclohexane 10653A~7 Examples ~5 to 50 AFFF agent compositions as listed in Table 7 have identical compositions with the exception of the anionic fluorinated surfactants of Type B, which vary from a perfluoro-hexyl to a per M uorooctyl, to a per n uorodecyl group and mixtures of Rf-groups as defined in Table 2. Lowest surface tension data are obtained with per M uorooctyl and a. mixed perfluoroalkyl group-containing nonionic surfactants of Type B. Similarly, these preferred compositions show the fastest film speed.
Most important of the results shown in Table 7 is the fact that an AFFF agent not containing any of the anionic fluorinated surfactant of Type B has much higher surface tensions;
therefore, a lower spreading coefficient, ro film resealing properties and, in addition, a very slow film speed.

10~53Z7 Examples 51 to ~7 Surface property measurements shown in Table 8 show that aqueous solutions of amphoteric Rf-surfactants of Type A, have low surface tensions, but high interfacial tensions (measured against hydrocarbons such as cyclohexane), and such aqueous solutions have, therefore, negative spreading co-efficients. By the addition Or amphoteric cosurfactants of Type C to aqueous solutions of amphoteric Rf-surfactants of Type A it is posæible to lower the interfacial tension properties and achieve these very high spreading coefficients.
Amphoteric cosurfactants of Type C are therefore referred to as interfacial tension depressants, even though they con-tribute to other properties of AFFF agents, such as foaming, stability, etc. Examples 51 to 56 show how the interfacial tension of a 0.1 percent aqueous solution of the amphoteric Rf-surfactant A5 is reduced by the addition of the preferred fatty aminimide surfactants of Type C, as listed in Table 3, from 7.1 dynes/cm to below 1.0 dynes/cm; the spreading co-efficient is increased from -1.1 dynes/cm to up to 5.6 dynes/cm. A typical nonionic surfactant, D4, is much less effective.

Table 7 Effect of Anionic X~-Surfactant and its ~omolog Content Example Nos. 45 to 50 Amphoteric Rf-Surfactant Solution Al: 4.93 % (30 % solids) Anionic Rf-Surfactant . . . . Various: 0.29 %
Amphoteric Cosurfactant . . . . . C2: 8.33 % (30 ~ solids) Other Amphoteric Cosurfactant . . C3: 1.66 % (70 % solids) ~onionic Cosurfactant . . . . . . D3: 2.97 % (70 % solids) Solvent . . . . . . . . . . . . . El: 5.00 %
Water . . . . . . . . . . . . . Balance Ex ~ple No. 45 46 47 40 ~9 50 Anionic Rf-surfactant, as noneB5 B6 B7 Bl B3 noted Rf-homolog C6 CO C10 mixture mixture Surface tension* dynes/cm 19.5 18.117.517.7 17.7 17-5 Interfacial tension* dynes/ 1.0 o.61.2 1.7 1.0 1.0 cm Spreading coefficient* 4.1 5.9 5'9 5.2 5.8 6.1 dynes/cm Film speed, sec very 13 5 38 9 5 slow Resealing propertynone eoodgood poorgoodgood *3 percent dilution in distilled water; interfscial tension against cyclohexane Table 8 Surface Properties of Amphoteric Rf-Surfactant/
Amphoteric Cosurfactsnt Solutions Amphoteric Rf-Surfactant Solution . . . A5: 0.1 %
Cosurfactants - Variable . . . . . . . . . 0.1 ~
Water .......................... Balance Surface Interfacial Tension Tension Spreading Example Cosurfactant dynes/cm dynes/cm Coefficient 51 none 18.6 7.1 - 1.1 52 C5 18.4 o.6 5.6 53 C6 18.8 o.6 5.2 54 C7 20.2 0.2 4.2 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 agents having a composition as listed in Table 9 are identical with the exception that the nonionic aliphatic cosurfactants of Type D vary. The comparison of the surface tension and interfacial tension data show that almost identical values within .5 of a dyne/cm are obtained and all samples show excellent compatibility with sea water while the only sample not containine nonionic hydrocarbon surfactant of Type D shows a heavy precipitate if diluted with sea water and aged at 65 C for 10 days.

10653'X7 Table 9 Composition and Evaluation Or ~FFF Agents Example ~os. 58 to 63 Amphoteric Rf-Surfactant Solution A7: 4.93 % ~30 'h solids) Anionic Rf-Surfactant. . . . . . . ~1: 0.29 %
Amphoteric Cosurfactant. . . . . . C2: 8.33 % (30 ~ solids) Other Amphoteric Cosurfactant. . . C3: 1.66 % ~50 ~, solids) Nonionic Cosurfactant. . . . .Various: 2.08 X (as 100 ~ solids) Solvent. . . . . . . . . . . . . . El: 5.00 %
Water. . . . . . . . . . . , . . . . . Balance _ _ _ _ .
Example No. ~ 58 59 60 61 62 63 .

Nonionic cosurfactant, as noted none D3 D5 C6 D7 D8 Surface tension* dynes/cm 18.0 17.3 17.4 17.0 16.9 17.5 Interfacial tension* dynes/cm 1.7 1.2 1.4 1.3 1.3 1.6 Spreading coefficient* dynes/cm 4.9 6.1 5.8 6.3 6.4 6.0 Compatibility with sea water heavy clear clear clear clear clear 6% dilution 65C for 10 days precipitate .
*3 percent dilution in distil7ed \later; interfacial tension aga~nst cylcohexane 10~53Z7 Examples 64 to 78 AFFF agents for 6 percent proportioning containing 2 percent by weight of variable solvents, but having otherwise identical compositions as shown in Table 10 were evaluated by using the Field Foam Test Method for determination of the foam expansion of a 6 percent dilution of the novel AFFF
agents in synthetic sea water. As the data in Table 10 show, it is possible to obtain expansion ratios ranging from 4.0 (high density foam) to 11.0 (lower density foam) by simply varying the type of solvent used in the AFFF agent. It is important from an ecological as well as economical standpoint that such a wide foam expansion range can be achieved with such a low (2 percent)solvent content.

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10653'~'7 Ex _nles 79 to 82 AFFF agents having co~positions as shown in Table 11 were evaluated and compared with a co~mercial AFFF agent, Light Water FC-200*, in 2.60 sq.m. fire tests. As the control time, ext~nguishine time, and burnback time data show, superior performance was achieved with the novel AFFF agents containing down to one-half the amount of fluorine in the product, and about equal control time, extinguishing time and burnback time was achieved in comparison to FC-200 with the AFFF agent Example 82 containing ~ust .8 percent fluorine vs. 2.1 percent fluorine in FC-200. These results indicate the higher effi-ciency of the novel AFFF agents, and that foam expansion is not as important a criterion to performance as are superior film properties.

*Trademark - 80 -10~53Z'7 Table 11 Comparative Fire Test Data* of AFFF Agents Example Nos. 79 to 82 . .
Amphoteric Rf-Surfactant Solution Al: Variable ( 30 % solids) ~onionic Cosurfactant . . . . . . Dl: Variable (100 % solids) Al-~ 4 (solids basis) Anionic Rf-Surfactant . . . . . . Bl: O. 35 % (100 % solids) Amphoteric Cosurfactant . . . . . Cl: 2.25 %
Solvent . . . . . . . . . . . . . E2: 6.25 %
Water . . . . . . . . . . . . . . Balance _ Example No. 79 80 81 82 FC-200 _ ~
Rf-surfactant A1, ~ as is 8.40 7.00 5.60 4.66 Nonionic surfactant Dl, % as i~ 1. 80 1.50 1.20 1.00 % F in formula 1.44 1.20 0.96 0.80 2.10 . .
Control time, sec 28 30 34 34 33 Extinguishing time, sec 44 34 47 51 52 Burnback time, min 8: 15 10: 30 5: 45 4: 58 5: 30 Foam expansion 5.5 5.6 5.4 4.7 7.0 25 % Drain time, min 4: 42 4 00 4: 15 3: 45 5: 03 * 6 ~ dilution in sea water, tested on 2.60 sq.m. fire ~ 81 10653'~7 Examples 83 to ô5 AFFF agents having the composition as sho~n in Table 12 with variable anionic Rf-surfactants of Type B and variable solvents of Type E or containing no solvent at all were evaluated in 2.60 sq.m. fire tests using 6.57 liters per minute nozzle. As the test data in Table 12 show, high density foams with a foam expansion of less than 5 and as low as 3.7 are obtained with AFFF agents not containing any solvent while a solvent content of 35 percent increases foam expansion to as high as 8.5 with this AFFF agent co~position. A comparison with the commercial FC-200 shows th~t slightly better extinguishing times are obtained in Example 83.

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10~;53~7 Exam~les 86 to 90 AFFF agents having a composition as shown in Table 13 were evaluated in 260 sq.m.fire tests. The performance of these AFTF agents containing different cosurfactants of Type C show excellent control times (as low as 26 seconds), very short extinguishing times (as low as 37 seconds), and two of the compositions (Examples 88 and 90) did extinguish the fire by itself shortly after removal of the pan used in the 2.60 sq.m. fire test, indicating the superior sealing capacity of the novel AFFF agents in comparison to the commercial products on the market.

Table 13 Compar~tive Fire Test Data* of AFFF Agents Exa~ple Nos. 86 to 90 -Amphoteric R -Surfactant Solution Al: 5.9 % ( 30% solids) Anionic Rf-Surfactant . . . . . . Bl: 0.35% (100% solids) Ionic (and Amphoteric) Cosurfactants . Variable Nonionic Cosurfactant Dl: 1.2 Solvent . . . . . . . . . . . . . E : 6.o Water . . . . . . . . . . . . . . Balance _ Example No. 86 87 88 89 90 . _ .
Cosurfactant - 1% solids C3 C4 Cl Cl Cl Cosurfactant - 2% solids C2 C2 C9 C10 C2 _ Control time, sec 26 27 33 33 26 Extinguishing time, sec 39 3~ 48 45 38 Burnback time, min 7:31 5:02 out 7:56 4:35 out Foam expansion 5.9 6.2 6.7 5.9 6.6 25% Drain time, ~in 5:19 _ 5:20 5:05 5:55 *Tested as a 6% dilution in sea water on 2.60 sq.m fires Fire completely extinguished _ 85 Example 91 An AFFF agent ha~ing the composition as shown in Table 14 was evaluated on a 117.05 sq.m. fire con-ducted on a level circular area 12.19 m in diameter fueled with 300 gallons of gasoline. A Rockwool FFF
nozzle with double screen uas used with a 189.27 1 per minute discharge. An excellent foam expansion of 9.0 was obtained and the fire was rapidly knocked down and almost completely extinguished within the diked area. Burnback was minimal and the "Su~mation of Percent Extinguishment" uas 320 far exceeding Mil Specifications F-24385 (Navy).

- 8~ -Table 14 Fire Test of Preferred AFFF Agent on 117.0 sq.m Fire Test Fxample No. 91 . _ _ Amphoteric Rf-Surfactant Solution Al: 5.93 % (30 % solids) Anionic Rf-Surfactant . . . . . . Bl: O.35 %
Amphoteric Cosurfactant . . . . . C2: 10.00 % (30 % solids) Other Amphoteric Cosurfactant . . Cl: 0.50 %
Nonionic Cosurfactant . . . . . . Dl: 1.20 %
Solvent . . . . . . . . . . . . . El: 6.oo %
Water . . . . . . . . . . . . . . . Balance Surface tension* dynes/cm. . . . 17.0 Interfacial tension* dynes/cm . . . 1.4 Spreading Coefficient* dynes/cm . . . 6.2 Fire test performance as a 6 percent sea water dilution Excellent knockdown and burnback "Su~mation of Percent Extinguishment" - 320 Foam expansion tl89.27 1 per minute nozzle) 9.0 25 % Drainage . . . . . . . . . . . . . . . 4:00 50 % Drainage . . . . . . . . . . . . . . . 8:41 .
*3 % dilution in distilled water; interfacial tension against cyclohexane 10~;5327 Example 8 92 to 96 AFFF agents having the compositions shown in Table 15 were tested as aerosol dispensed AFFF agents upon 2B fires (Underwriters Laboratory designation). The results show that the compositions were more effective in extinguishing the fires in a shorter time than either of the commercially available agents, Light Water FC-200 or FC-206. Example 94 shows that a composition protected against freezing iB also effective as an extinguisher.

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10653~7 Footnotes to Table 15 The % solvent content and % buffer salts are noted for the actual aerosol charge after dilution of the concentrate to a 6% dilution;
the remainder is water 2The aerosol container is a standard can containing a 430 gram charge of AFFF agent and a 48 gram charge of dichlorodifluoro-methane Buffer salts are Fl, Sorensen's phosphate at pH 7.5 F2, Sorensen*s phosphate at pH 5.5 F3, McIlva~ne's citrate/phosphate at pH 5.5 F4, Walpole's acetate at pH 5.5 6.o~ dilution in distilled water; interfacial tension against cyclo-hexane 5discharge duration, sec - time to discharge aerosol completely at 21.1C
foam volume, liters - total foam volume immediately a M er discharge control time, sec - time at which fire is secured, althougb still burning extinguishing time, sec - time for total extinguishment 62B fire - a 0.465 sq. meters area fire *Trademarks - 90 iO653z~

Ex~mples 97 and 98 AFFF agents having the composition shown in Table 16 were compared to commercially available AFFF agents of both 6 percent and 3 percent proportioning types - 3M's Light Water FC-206 and FC-203 and National Foam's Aer-0-Water*6 and 3. The Examples 97 and 98 both demonstrate vastly superior film speeds (time to 50 percent seal), as well as more complete and highly persistent seals than available AFFF agents. These factors are of fundamental importance for an effective AFFF composition.

*Trademark - 91 10653~
~able 16 Sealing Characteristics of AFFF Compositions Example Nos. 97 and 98 Amphoteric Rf-Surfactant Solution A1: 5.0 % (30 % solids) Anionic Rf-Surfactant . . . . . . Bl: 0.3 %
Amphoteric Cosurfactant . . . . . C2: 8.3 % (30 % solids) Other Ionic Cosurfactants . . . . . . Variable Nonionic Cosurfactant . . . . . . . . Variable Solvent . . . . . . . . . . . . . El: 5.00 %
Water . . . . . . . . . . . . . . . . Balance .
Aer-O-Water Aer-O-Water FC FC
Example No. 97 g8 6 3 206 203 . .
Cosurfactant Cl 0.4 --Cosurfactant C4 -- 0.4 Cosurfactant D3 3.0 --Cosurfactant Dl -- 2.1 Time to 50~ seal 5 8 18 18 25 12 % seal in 30 sec 98 97 45 30 85 72 % seal in 120 sec98 98 87 91 96 87 Surface area - 20 cm2 Delivery rate - 0.17 ml/min Wave number _ 2930 cm 1 Cell path length - 3 cm Helium flow rate - 1000 ml/min 10653~7 .

Examples 99 to 103 AFFF agents having compositions as shown in Table 17 were submitted to fish toxicity studies using fathead minnows and bluegills. The evaluated AFFF agents have, as the results show, considerably lower toxicity than the control (Light Water FC-200) and, in addition, show a considerably lower chemical oxygen demand than the control primarily because of the lower solvent content in the novel AFFF agents.

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but with otherwise identical compositions, were evaluated. The comparative evaluation data in Table 18 show (a) that 3 percent solutions of the listed AF~F agents have spre~ding coefficients ranging from 4.5 to 5.8 dynes/cm, and (b) that the concentrates per se have a fish toxicity (fathead minnows) ranging from 114 to 524 ppm for a TL50, indicating that the listed AFFF agents are considerably less toxic than Light Water FC-200, having a TL50 of 79 ppm. Table 18 also shows that the listed AFFF agents have considerably lower chemical and biological oxygen demands (COD and BOD5) than FC-200.

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- 9 1~ -~ -Example~ 109 to 113 Further optimized AFFF agents for 6 percent proportion-ing containing different types and amounts of amphoteric and nonionic cosurfactants of Types C and D, but identical a~photeric and anionic Rf-surfactants of Types A and B, were evaluated. The comparative evaluation data in Table 19 show that spreading co-efficients ranging from 3.6 to 5.1 dynes/cm are obtained, while fish toxicity data of the AFFF agent concentrates range from 294 to larger than 1000 ppm for a TL50 for fathead minnows.
A TL50 f larger than 1000 ppm is considered non-toxic ard products like AFFF agents Examples 112 and 113 are therefore most desirable from an ecology standpoint. Also listed in Table 19 are the chemic~l and biologica] oxygen demands (COD, BOD5) of Examples 110 to 113. The very low COD Values ranging from 0.19 to 0.22 g. of oxygen per liter are primarily due to the low solvent content in the novel AFFF agents.

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CQ ~ q l ~1 ~ E-~ rl ~ ~d F l h h h ~I h 6-~ ~ h q ~ Oâ â
~ C~ ~ H ~ m _ ~8 Example 114 An AFFF agent having a composition as sho~m for Example 112 and solutions thereof in synthetic sea water were selected to show the low or non corrosive character of the novel AFFF agents. Corrosion tests carried out in accordance with U.S.
military requirement MIL-F-24385 Amendment 8, June 20, 1974 show, as presented in Table 20, that corrosion observed with different metals and alloys is 10 to 100 times smaller than the maximum tolerance levels specified in MIL-F-24385, Amendment ô.

_ 99 _ 10~;53,'~7 o o~0~ ~ ,,.a~ ~q~
N ~ ~ O ~ . .,~ ~ ~
~ ~ 3 ~ x ~ ~ ~ ~ ~
~ I~ C~ ~i ~; ~i ~i s~i ~

~ ~ o~ C0~ ~X

~I nXt O O O 01 O O 0 0 o~
æ _ . _ ~ ~D CU 0~ ~ X
~ ~ h r-l C`J ~t ~ ~fl P~ ~1 ~ .~ O O O ol O o ol ~ ~i ~
. .~ .

q~ r ,_ ~h, æ
~ ~ ~ ~ ~ ~ ~ ,, C~ o ~ o rl ~ o o ~ ~ ~ ~ o ~ u~ ~ g d ~ ~ ~ O
O ~ ~ O -~ O ~
~ Q~ o ~ ~ 1 ::~~ rl ~ E~ d ~n ~ _ ,1 ~ ~
~ oh Q~ O ~ 0 ~ ~ ~3 ~a ~ O oh o ~ C) o ~ ~ C) oO O ~ ~O :t ~ ~ SO ~ ~ d ~ ~ h ~*~*~ ~O .h h ~I g~ O O ~ O ~ ~ ~ ~1 . ~ 1 h ,I h O O ~ h ~ O
!i ~ CO _~ rl q~ h ~ ~ ~ ~ q~ o ~ q~
tl ~ rr~ ~ ~ ~ ~ S~ ~ ~ ~ ~ ~ ~ O O ~ ~ O
O ~ ~ h ~ ~ ~ ~ O ~ ~ O
r l UJ ~ ~ ~ ~ . ~ ~ d) 0 CJ ~J N U~ rl ~ a~ ~1 o ~ ~ a ~ ~ ~ ~ ~ æ æ æ ~ .~ O ~ ~
~ ~ ~~ c~ ~ ~ ,1 ~ ~ H ~ ~
0 ~3 co g g ~ g O ~ O O O O O ~ ~ O ~ ~ h o~ o~ o~ o~ ~ æ ,~ C~J *
C ~i ~

~O~;S3~7 EXamples 115 to 117 AFFF agents were formulated containing identical ingredients but at progressively higher concentrations. The data show that concentrates can be prepared for 3 percent, and even 1 percent proportioning, which are stable 5 and perform well. Six percent proportioning concentrates such as National Foam, Aer-0-Water 6 and Light Water FC-200 containing 18 percent and 34 per-cent, respectively, of sclvents, contain so much solvent that they could not be formulated as 1 percent proportioning concentrates.

Table 21 Formulation of Highly Concentrated AFFF Agents Example Nos. 115 to 117 . _ Example No.115 116 117 Proportioning Type ~ .3~ l 1~
_ % as is % solids % as is % solids % as is % solids Amphoteric Rf-surfactant Al 3. 33 l . oo6.66 2.00 20.0 6. o Anionic Rf-surfactant B2 0.80 0.20 1. 60 o .40 4. 80 1.20 Amphoteric cosurfactant C12 1.70 1. 703. 40 3. 40 10.20 10.20 Nonionic cosurfactant Dl 0.50 0.50 1.00 l.Oo 3.00 3.00 Solvent 6. oo __ 12.00 __ 36.00 __ Water 87. 67 __ 75.34 __ 26.00 __ Total 100.00 3.40100.00 6.30100 0020 40 Freezing point C -3 -7 -12 pH 7.5 7.5 7.5 Chloride content (ppm) ~5 '50 <5o

Claims (43)

1. Fluorinated compounds of the formulae I

II and III
wherein Rf is straight or branched chain perfluoro-alkyl of 1 to 18 carbon atoms or said perfluoroalkyl substituted by perfluoroalkoxy of 2 to 6 carbon atoms;
R1 is branched or straight chain alkylene of 1 to 12 carbon atoms, alkylenethioalkylene of 2 to 12 carbon atoms, alkyleneoxyalkylene of 2 to 12 carbon atoms or alkyleneiminoalkylene of 2 to 12 carbon atoms where the nitrogen atom contains as a third substituent, hydrogen or alkyl of 1 to 6 carbon atoms;
y is 1 or zero;
X is oxygen or -NR-, wherein R is hydrogen, alkyl of 1 to 6 carbon atoms, hydroxyalkyl of 1 to 6 carbon atoms, or X together with Q forms a piperazine ring; and Q is a nitrosen containing group selected from (1) an aliphatic amino group selected from (1a) (1b) and (1c) wherein R2 is a 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;
k is l or zero, with the proviso, that if X
is oxygen, k is l;
R3 and R4 are independently of each other hydrogen, alkyl or substituted alkyl group of 1 to 20 carbon atoms; phenyl group, alkyl or halogen substituted phenyl group of 6 to 20 carbon atoms; polyethoxy or polypropoxy group of 2 to 20 alkoxy units with the proviso that if X is oxygen, R3 and R4 are not hydrogen;
R5 is hydrogen, an alkyl group or hydroxyalkyl group, aralkyl or a group of the formula -(CH2)n-COO-alkyl, said alkyl group having 1 to 18 carbons;

G? is selected from the groups -(CH2)n-COO?; -(CH2)3SO3?;

and where n is 1 to 5;

(2) cyclic amino groups selected from (2a) (2b) A? and (2C) wherein Y is a diradical of the formulae -(CH2)4--(CH2)5--(CH2)2-O-(CH2)2- or wherein R2, R5, A? and G? are as defined above, R7 and R8 are independently hydrogen, a lower alkyl or hydroxy-lower alkyl group of 1 to 6 carbon atoms, with the proviso, that if X is oxygen, R8 cannot be hydrogen;

(3) aromatic amino groups selected from (3a) (3b) and (3c) (4) fused-ring amino group selected from (4a) (4b) and (4c) wherein Z is halogen or methyl, a + b is an integer from 0 to 3; and (5) heterocyclic amino group of the formula (5a) -(R2)k-E
(5b) -(R2)k-E?-R5 A?
(5c) -(R2)k-E?-G?
where k is one or zero and E is selected from N-hydroxyalkyl or N-amino-alkyl substituted pyrrolyl, pyrazolyl, imidazolyl, triazolyl, indolyl or indazolyl, hydroxyalkyl and aminoalkyl ring-substituted pyridazinyl, pyrimidinyl, pyrazinyl or quin-oxalinyl.

2. Compounds of Claim 1 of structures I and II
wherein Q is selected from structures (1) and (2).

3. Compounds of Claim 1 of structures I and II
wherein Q is selected from structures (1a), (2a) and (3a).

4. Compounds of Claim 3 wherein R1 is alkylene, R2 is straight or branched chain alkylene of 2 to 5 carbon atoms, y is zero, R3 and R4 are alkyl group of 1 to 20 carbons or alkyl group substituted with hydroxyl, polyethoxy group having 2 to 20 ethoxy units or a group R7 is hydrogen, R8 is lower alkyl or hydroxy substituted lower alkyl, a is zero.

5. Compounds of Claim 4 wherein Q is k is one, R3 and R4 are independently alkyl of 1 to 5 carbons, X is oxygen or -NR- where R is hydrogen or alkyl of 1 to 3 carbons.

6. Compounds of Claim 5 wherein R1 is ethylene R2 is straight chain alkylene of 2 to 5 carbon atoms, and R3 and R4 are methyl or ethyl.

7. Compounds of Claim 4 wherein Q is where R2 is straight chain alkylene of 2 to 5 carbon atoms.

8. Compounds of Claim 4 wherein Q is where R2 is straight chain alkylene of 2 to 5 carbon atoms, k is 1 and a is zero.

9. Compounds of Claim 1 having the structure where R1 is alkylene, R2 is straight or branched chain alkylene of 2 to 5 carbon atoms, y is zero, and Q has the structure (1a), (2a) or (3a).

10. Compounds of Claim 9, wherein Q has the struc-tures (1) or (2).

11. Compounds of Claim 1 of structures I and II
wherein Q is selected from structures (1b), (2b) and (3b).

12. Compounds of Claim 11, wherein R1 is alkylene, R2 is straight or branched chain alkylene of 2 to 5 carbon atoms, y is zero, R3 and R4 are alkyl group of 1 to 20 carbons or alkyl group substituted with hydroxyl, polyethoxy group having 2 to 20 ethoxy units or a group R7 is hydrogen, R8 is lower alkyl or hydroxy substituted lower alkyl, a is zero.

13. Compounds of Claim 12 wherein A? is selected from Cl?, Br?, CH3CH2OSO3? and CH3OSO3?, and R5 is selected from methyl, ethyl, propyl, butyl and benzyl.

14. Compounds of Claim 1 having the structure where R1 is alkylene, R2 is straight or branched chain alkylene of 2 to 5 carbon atoms, y is zero, and Q has the structure (1b), (2b) or (3b).

15. Compounds of Claim 1 of structures I and II
wherein Q is selected from structures (1c), (2c) and (3c).

16. Compounds of Claim 15 wherein R1 is alkylene, R2 is straight or branchcd chain alkylene of 2 to 5 carbon atoms, y is zero, R3 and R4 are alkyl group of 1 to 20 carbons or alkyl group substituted with hydroxyl, polyethoxy group having 2 to 20 ethoxy units or a group R7 is hydrogen, R8 is lower alkyl or hydroxy substituted lower alkyl, a is zero.

17. Compounds of Claim 16 wherein G? is selected from -(CH2)2-COO? and -(CH2)3SO3?

18. Compounds of Claim 1 having the structure where R1 is alkylene, R2 is straight or branched chain alkylene of 2 to 5 carbon atoms, y is zero, and Q has the structure (1c), (2c) or (3c).

19. Compound of Claim 1 which is and its isomer.

20. Compounds of Claim 1 which are and their isomers wherein about 25% of Rf are alkyl groups of 6 carbon atoms, about 50% of Rf are alkyl groups of 8 carbon atoms and about 25% of Rf are alkyl groups of 10 carbon atoms.

21. Compounds of Claim 1 which are and their isomers wherein about 25% of Rf are alkyl groups of 6 carbon atoms, about 50% of Rf are alkyl groups of 8 carbon atoms and about 25% of Rf are alkyl groups of 10 carbon atoms.

22. Compounds of Claim 1 which is and their isomers wherein about 25% of Rf are alkyl groups of 6 carbon atoms, about 50% of Rf are alkyl groups of 8 carbon atoms and about 25% of Rf are alkyl groups of 10 carbon atoms.

23. Compounds of Claim 1 which are and their isomers wherein about 25% of Rf are alkyl groups of 6 carbon atoms, about 50% of Rf are alkyl groups of 8 carbon atoms and about 25% of Rf are alkyl groups of 10 carbon atoms.

24. Compounds of Claim 1 which is and its isomer.

25. Compounds of Claim 1 which is and its isomers.

26. Compounds fo Claim 1 which is and its isomers.

27. Compounds of Claim 1 which is and its isomers.

28. Compounds of Claim 1 which is and its isomers.

29. Compounds of Claim 1 which is and their isomers wherein about 25% of Rf are alkyl groups of 6 carbon atoms, about 50% of Rf are alkyl groups of 8 carbon atoms and about 25% of Rf are alkyl groups of 10 carbon atoms.

30. Compounds of Claim 1 which is and their isomers wherein about 25% of Rf are alkyl groups of 6 carbon atoms, about 50% of Rf are alkyl groups of 8 carbon atoms and about 25% of Rf are alkyl groups of 10 carbon atoms.

31. Compounds of Claim 1 which is and its isomers.

32. Compounds of Claim 1 which is and its isomer.

33. Compounds of Claim 1 which is and its isomer.

34. Compounds of Claim 1 which is and its isomer.

35. A compound selected from the formulae and its isomer or wherein Rf is straight or branched chain perfluoro-alkyl of 1 to 18 carbon atoms or said perfluoroalkyl substituted by perfluoroalkoxy of 2 to 6 carbon atoms;
R1 is branched or straight chain alkylene of 1 to 12 carbon atoms, alkylenethioalkylene of 2 to 12 carbon atoms, alkyleneoxyalkylene of 2 to 12 carbon atoms or alkyleneiminoalkylene of 2 to 12 carbon atoms where the nitrogen atom contains as a third substituent, hydrogen or alkyl of 1 to 6 carbon atoms;
y is 1 or zero;
X is oxygen or -NR-, wherein R is hydrogen, alkyl of 1 to 6 carbon atoms, hydroxyalkyl of 1 to 6 carbon atoms;
T is a nitrogen containing divalent group selected from (1) (2) (3) wherein R9 is an aliphatic hydro-carbon triradical of 3 to 19 carbon atoms, preferably of 3 to 5 carbons.

36. A compound of Claim 35 wherein R1 is alkylene.

37. An aqueous film forming concentrate composition for extinguishing or preventing fires by suppressing the vaporization of flammable liquids, said composition comprising A) 0.5 to 25 % by weight of a fluorinated compound of any one of the formulae I to III defined in claim 1, B) 0.1 to 5% by weight of anionic fluorinated sur-factant, C) 0.1 to 25% by weight of ionic non-fluorochemical surfactant, D) 0.1 to 40% by weight of nonionic non-fluorochemical surfactant, E) 0 to 70% by weight of solvent, and F) water in the amount to make up the balance of 100%,

38. A composition of claim 37 wherein B) the anionic fluorinated surfactant is represented by the formula RfQmZ
wherein Rf is a fluorinated saturated monovalent non-aromatic radical containing from 3 to 20 carbon atoms in which the carbon atoms of the chain are substituted only by fluorine, chlorine or hydrogen atoms with no more than one hydrogen or chlorine atom for every two carbon atoms, and in which a divalent oxygen or trivalent nitrogen atom, bonded only to carbon atoms, can be present in the skeletal chain;
Qm, where m is an integer of 0 or 1, is a multi-valent linking group comprising alkylene, sulfonamido alkylene and carbonamido alkylene radicals; and Z is a water solubilizing polar group comprising anionic radicals;
C) the ionic non-fluorochemical sur-factant is selected from carboxylic acids, sulfuric esters, alkane sulfonic acids, alkylaromatic sulfonic acids, phosphates and phosphonic acids, thiosulfates and sulfinic acids;
D) the nonionic non-fluorochemical surfactant is select-ed from polyoxyethylene derivatives of alkylphenols, linear or branched alcohols, fatty acids, mercaptans, alkylamines, alkylamides, acetylenic glycols, phos-phorus compounds, glucosides, fats and oils, amine oxides, phosphine oxides those derived from block polymers containing polyoxyethylene and/or poly-oxypropylene units, and E) the solvent is selected from 1-butoxyethoxy-2-propanol, hexylene glycol and diethylene glycol monobutyl ether.

39. A composition of claim 38 consisting essentially of A) 1.0 to 3.5% by weight of amphoteric fluorinat-ed surfactant, B) 0.1 to 2.5% by weight of anionic fluorinated surfactant, C) 0.1 to 4.0% by weight of ionic non-fluorochemical surfactant, D) 0.1 to 8.0% by weight of nonionic non-fluoro-chemical surfactant, E) 0 to 20% by weight of solvent and water in the amount to make up the balance of 100%

40. A composition of claim 39 consisting essentially of A) N-[3-(dimethylamino)propyl]-2 and 3-(1,1,2,2-tetra-hydroperfluoroalkythio) succinamic acid B) perfluoroalkanoic acid or potassium salt thereof C) partial sodium salt of N-lauryl .beta.-iminodipropionic acid D) octylphenoxypolyethoxyethanol and E) 1-butoxyethoxy-2-propanol .

41. A composition of claim 39 consisting essentially of A) N-[3-(dimethylamino)propyl]-2 and 3-(1,1,2,2,-tetrahydroperfluoroalkythio) succinamic acid B) perfluoroalkanoic acid or potassium salt thereof C) partial sodium salt of N-lauryl .beta.-iminodipropionic acid and cocoimidazolinium ethosulfate D) octylphenoxypolyethoxyethanol and E) 1-butoxyethoxy-2-propanol

42. An aqueous film-forming composition for extinguishing or preventing fires in an aerosol form, which comprises said composition of claim 37, diluted with water and an inert propellant.

43. An aqueous film-forming composition for extinguishing or preventing fires which comprises said composition of claim 37, diluted with water.