DE2559189A1 - FLUORINE COMPOUNDS - Google Patents

Description

Case 61-9738 / 9837 / GC 716/721 Germany

Fluorinated compounds

609828/1043

CIBA-GEIGY AG, CH-4002 Basel V j »L ^" v * " ⁷ -" i "χ ί ILI I *

1 2559183

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

Various fluorinated, amphoteric and cationic surfactants are known from U.S. Patents 2,764,602, 3,555,089 and 3 681 413 and German disclosure documents 2 120 868, 2 127 232, 2 165 057 and 2 315 326 became known. Although the compounds of the present invention also contain R-, groups contain, they differ significantly from the surfactants disclosed in the patents cited above.

Intermediate products suitable for preparing the surfactants of the invention are disclosed in U.S. 3,471,518 wherein the addition of R ~ -alkylenethiols to maleic acid and

60 98 28/1043

Maleinate is described, and in US 3,706,787, which describes the addition products of R _f -thiols to dialkyl and monoalkyl maleate are given. German Offenlegungsschrift 2 219 642 discloses R ~ -alkylenethiol addition products with dialkylaminoalkyl acrylates and methacrylates; these compounds are cation-active surfactants and do not contain any 1,2-dicarboxylic acid. While all fluorinated amphoteric surfactants of the prior art are synthesized by quaternizing a corresponding tertiary amine with an alkylating agent such as lactones, sultones or halogenated acids, the amphoteric surfactants according to the invention are produced by a simple ring-opening reaction without the use of possibly carcinogenic alkylating agents. The surfactants according to the invention are excellent wetting agents, especially when used in combination with other fluorinated and non-fluorinated surfactants. Furthermore, they can be manufactured much more economically and safely.

The present invention relates to novel fluorinated compounds, which are preferably amphoteric or are cation-active and have good surface-active properties, and a process for their preparation, The fluorinated compounds correspond to the formulas

R.-R ¹ - ^ - (CH) -CH COOH _T

f 2 y j · I

—COX-Q

and its isomer

- 3 -6098 28/1043

y-cii-cox- Q _ττ

-CH C C

^Y 1>

~ Q III

wherein R ,, straight-chain or branched perfluoroalkyl with 1 to 18 carbon atoms or such perfluoroalkyl substituted by perfluoroalkoxy with 2 to 6 carbon atoms,

R branched or straight-chain alkylene with 1 to 12 carbon atoms, alkylene thioboalkylene with 2 to 12 carbon atoms, alkyleneoxyalkylene with 2 to 12 carbon atoms or alkyleneiminoalkylene with 2 to 12 carbon atoms, in which the nitrogen atom contains hydrogen or alkyl with 1 to 6 carbon atoms as the third substituent,
y 1 or zero,

X is oxygen or -NR, in which .R is hydrogen, lower alkyl having 1 to 6 carbon atoms or hydroxyalkyl having 1 to 6 carbon atoms is, or X forms a piperazine ring together with Q, and

Q represents a nitrogen-containing group selected from (l) one of

_ 4 609828/1043

(la)

(Ib)

-and • R '

(lc)

selected aliphatic amino groups wherein

R for linear or branched alkylene with 2 Ms 12 carbon atoms, linear or branched alkylene interrupted by oxygen or sulfur with up to 60 carbon

atoms or hydroxyl-substituted alkylene, where R is preferred is straight-chain or branched alkylene with 2 to 5 carbon atoms,

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

Rr and R independently of one another each represent hydrogen, an alkyl group or substituted alkyl group with 1 to 20 carbon atoms, a phenyl group, an alkyl or halogen substituted one Phenyl group with 6 to 20 carbon atoms, polyethoxy or polypropoxy group with 2 to 20 alkoxy units, with the proviso that R ^ and R are not hydrogen when X is oxygen and where alkyl is 1 to 5

_ 5 - BQ982B / 1043

Carbon atoms, diejiyl, hydroxyl, carboxyl, halogen, Alkylene dialkyl phosphonate such as methylene diethyl phosphonate or a group

-N

as substituents on alkyl, and methyl, halogen or hydroxyl

-z. as substituents on phenyl come into question and R ^ and R

are preferably alkyl groups with 1 to 4 carbons, A ^ for any anion which forms an ammonium salt of the formula NH ^ A ⁰ ^ and is derived from alkyl halides, benzene or chlorobenzenesulfonate esters of alkyl alcohols and methyl and ethyl sulfates, where A is preferably Cl ^ , Br,

CH ^ CH ₀ OSO, © or CH _x OSO, Θ is, 3 2 3 3 3

R- ^ for hydrogen, an alkyl group or hydroxyalkyl group, aralkyl or groups of the formula - (CHp) -COO-alkyl, wherein said alkyl group has 1 to 18 carbon atoms and R- ^{7 is} preferably methyl, ethyl, propyl, butyl or benzyl, and
G ^ for one among the groups

; - (CH ₂ ) ₃ SO ₃ ⁰ ·,

-CH- COO and -C-COO

¹ I!

• CH ₂ -COOH CH-COOH

selected group wherein η is 1 to 5; (2) under

609828 / i "ü43

(2a) -R -N ^ Y

(2b) -R ² -n ⁰ Y Α ^{Θ xma}

• I ⁵

(2c)

selected cyclic amino groups, in which Y is a diradical group of the formulas:

- (CH ₂ ) ₄ -, - (CH ₂ ) ₅ -, - (CH ₂ ) ₂ -0- (CH ₂ ) ₂ - and

- (CH ₂ ) -CH-N- (CH ₂ ) ₂ -, where R ² , R ⁵ , i3 and G ^ have the above-R? R ⁸

have given meaning, and 7 R

R and R independently hydrogen or a lower alkyl or represent hydroxy-lower alkyl groups having 1 to 6 carbon atoms, with the proviso that R is not hydrogen may be when X is oxygen; (3) under -

(3b)

and

609828/1043

(3c)

- (R ² )

selected aromatic amino groups and

(4) under ia _Zb

(4a)

(4b)

(4c)

selected ring-fused aromatic amino groups, wherein Z is halogen or methyl and a + b is an integer from 0-3; and

(5) a heterocyclic amino group of the formula (5a) - (R ² ) _k -E

(5b)

609828/1043

(5c) - (R ^) _k -E ^ -i where k is one or zero and

E under N-hydroxyalkyl- or N-aminoalkyl-substituted Pyrrolyl, pyrazolyl, imidazolyl, triazolyl, indolyl or indazolyl or ring-substituted by hydroxyalkyl and aminoalkyl Pyridazinyl, pyrimidinyl, pyrazinyl or quinoxalinyl is selected.

The present invention also relates to aqueous film-forming concentrates for extinguishing fires or -Prevention by suppressing the evaporation of flammable liquids, as well as a method of fire fighting (Deletion or prevention) in which these concentrates are used.

The compounds represented by the above formulas I and II, where Q represents the constitutions (la), (2a), (3a), (4a) or (5a) are in solution in the form of their internal salts of the general formulas

R ^ -R-S- (CH_) -CH COO®

. ^{2 y} I © Ia CH- COX-QH

- - ' and

) -CH-COX-OH

and are therefore amphoteric surfactants.

Compounds of the formula III are obtained by imidating compounds of the constitutions I and II with

- 9 - GO 9 8 2 δ / i υ 4 3

X = -NH- by heating, either as such or in solution, to a temperature in the range from 50 to 150 C or preferably to a temperature of about IGG ⁰ C. The compounds according to the invention in which Q the constitutions (Ia), ( 2a), (3a), (4a) or (5a) are prepared from maleic, itaconic anhydrides, perfluoroalkyl-containing thiols and a polyamine or amino alcohol. They are typically prepared in two stages: first, maleic anhydride or itacionic anhydride is reacted with an equimolar amount of either an alcohol containing at least one tertiary amino group or a primary or secondary amine containing at least one other primary, secondary or tertiary amino group to form a intermediate unsaturated half-ester or half-amide of the constitutions: ^

CO (P
HC

^c or

COX-QH

² I Θ

CH ₂ -COa-QH

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

Compounds of this constitution are described in the literature as comonomers for vinyl polymerization, for example in U.S. 2,821,521

- 10 609828/1043

I '© ■

CH-CONH (CH): i (CHO ₀ H

N- (3-Dimethylaminopropyl) maleic acid amide.

For compounds in which X -N-CH-, or -NC _O H _C

i 3 »25

and Q is -CH ₂ CH ₂ -N (CH ₃ ) ₂ , the intermediate is cyclized to form a compound of the constitution:

CH.
³

S CH.COO ^

H [2

^ = • 0
N

CH ₃ (or -C ₂ H ₅ )

These are new compounds, and their constitutions were established by NMR and the absence of acidic water confirmed.

Instead of producing the intermediate product from the anhydride by ring opening, other synthetic routes can be used, such as, for example, transesterification or transamidation of a maleic, fumaric or itaPonic acid lower alkyl half-ester.

The synthesis of the new surfactants is completed in a second reaction stage, during which the perfluoroalkyl-substituted Thiol is added to the double bond of the intermediate by base catalysis. These

- 11 -

6 0 9 8 2b / 1043

The reaction normally proceeds at room temperature, except when there is an intermediate of the cyclic described above Type forms; in this case, the addition of the thiol takes place only at temperatures of 85 ° C and above.

On the other hand, one can reverse the synthesis route and
add the R ~ thiol to the unsaturated cyclic anhydride or its lower alkyl half ester by base catalysis or a radical mechanism. The intermediate is then mixed with at least one tertiary amino group containing
Alcohol or a primary or secondary amine containing at least one further primary, secondary or tertiary amino group reacted, with the desired product
receives. Because of the high yield and purity of the product, the first synthetic route is preferred.

The monoesters can be easily converted through
the equimolar amount of an unsaturated cyclic anhydride and the amino alcohol, either undiluted or in solution,
synthesize. The monoamides can be obtained by implementing
produce equimolar amounts of an unsaturated cyclic anhydride with a polyamine at a temperature below 5O ⁰ C in a solvent. Solvents such as methyl ethyl ketone, diethylene glycol dimethyl ether, dimethylformamide, tetrahydrofuran, perchlorethylene, 1,1,1-trichloroethane, dichloromethane, dioxane, dimethyl sulfoxide and N-methylpyrrolidone are possible. As described in more detail in Canadian Patent 828 195, the amides are also in water or a mixture of water and a solvent listed above

G098 28 /

The anhydride can be added to the aqueous solution of the amine.

The addition of the FU-substituted thiol to the monoesters and monoamides occurs in solution or undiluted carried out at a temperature between 20 and 100 ° C. In Solvents to be considered are alcohols such as methanol, ethanol, n-propanol, isopropanol, n- and isobutanol, amyl alcohol, n-hexanol, cyclohexane, benzyl alcohol, etc .; Ethers such as dimethyl ether, methyl ethyl ether, diethyl ether, di-npropyl ether, Diisopropyl ether, methyl n-butyl ether, ethyl n-butyl ether, Ethylene glycol dimethyl ether, divinyl ether, D.iallyl ether, tetrahydrofuran, etc .; Ketones such as acetone, Methyl ethyl ketone, methyl n-propyl ketone, diethyl ketone, Hexanone-2, hexanone-3 »methyl-t-butyl ketone, di-n-propyl ketone, Diisopropyl ketone, diisobutyl ketone, chloroacetone, diacetyl, acetylacetone, mesityl oxide, cyclohexanone, etc .; N-methylpyrrolidone, Dimethylformamide, acetonitrile, benzene, chlorobenzene, chloroform, methylene chloride, carbon tetrachloride, Dioxane, nitrobenzene, toluene, etc. It is also possible to use water or a mixture of water and any of the foregoing Use solvent.

Methanol, ethanol, isopropanol,

Diethylene glycol monomethyl ether or diethylene glycol methyl butyl ether and solvent mixtures containing water are preferred. If it is necessary for a follow-up reaction, For example, quaternization with propane sultone to remove the alcohol, a mixture of N-methylpyrrolidone and a low boiling alcohol such as methanol

809828/1043

- 13 -

preferred. Since the times one acid mono ester or maleic acid monoamides already contain an amino group, there is no need to add any further amine as a catalyst for the addition of thiols.

The new surfactants obtained in this way are readily soluble in water or water / auxiliary solvent mixtures, and the solutions are essentially neutral. In dilute aqueous solution, the tertiary aminoalkyl monoesters and -monoamide polymeric aggregates, resulting in very high viscosities leads; These gel-like solutions can be by adding an auxiliary solvent such as butyl carbitol or a non-ionic auxiliary surfactant such as an ethoxylated alkylphenol break up easily.

The compounds according to the invention in which Q corresponds to the constitutions (lb and c), (2b and c), (3b and c), (4b and c) and (5b and c) is obtained by quaternizing the amphoteric surfactants prepared as described above.

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

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

If an inert solvent is used, the quaternary ammonium compounds obtained fall often as solids. They are easy to detach, wash and dry. One solution can be used to

6 0 9 8 2 8 /

products, as known to those skilled in the art, by adding a nonsolvent isolate. If desired, the products can be obtained by recrystallization from a suitable one Further clean the solvent or solvent mixture. Products obtained as viscous liquids can through Extraction can be further purified with a suitable solvent.

If the amino alcohol is a diol or at least three amino groups, of which at least two are primary or secondary are, containing polyamine, you can do it with two moles of maleic or ItaQonsäureanhydrid and two moles of R ~ -alkylenethiol convert so that bis-R ^ -alkylenethiosuccinic acid half-amides, -haibester and -succinimide arise, which are represented by the formulas

R _f -R -S- (CH ₂ ) -CH-COOK

CH ₂ COX

and its isomer or

1 (CH ₂ ) _v H . N— ^R f " H C-C -S-

-T

-J 2

wherein T is a divalent nitrogen-containing group selected from

- 15 609828/1 043

(D - _R 2. _N

V, -

2 / ^

(2) -R -N H N-R

v /

(3)

wherein R is the tri-radical of an aliphatic hydrocarbon having 3 to 10 carbon atoms, preferably 3 to 5 carbons, can be represented. An example of formula (3) is 3-pyridylpropane-1,3-diradical.

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

(D .R ³

H0-R ² -N

wherein R ^ and R have the meaning given above, from.

Examples to illustrate the alcohols listed above are.

HO-CH ₂ -CH ₂ -N (CH ₃ ).

HO-CH ₂ -CH ₂ -N (C ₂ H ₅ )

HO- (CH ₂ J ₃ -N (CH ₃ )

HO-

HO- (CH ₂ ) ₃ -N (C ₃ H ₇ ) ₂

- 16 -

60 9828/1043

KO- (CH ₂ ) ₄ -N (CH ₃ ) HO (CH ₂ ) ₅ -N (CH ₃ ) HO- (CH ₂ ) ₆ -N (CH ₃ ) HO (CH ₂ ) ₈ -N (CH ₃ ^ HO (CH ₂ ) ₁₀ -HO (CH ₂ ) ₁₂ -N (CH ₃ )

HO-CH-CH N (CH) CH ₃

with χ + y = 3-25 and ζ = ϊ-20

HO-CH ₀ Cli-K (phenyl) ai_CH, OH HO-CH ₂ CH ₂ -Il (tolyl) CH ₂ CH ₂ OH HO-CH-CH ₉ -N (phenyl) CH _n CH-OH

CH ₃ (CK ₂ CH ₂ O) H

HIGH ₂ CH ₂ -N-CH CH OH

°° 2 ^Β 5

OC ₂ H ₅

Cyclic compounds of the formula

(2) H0-R ² -NY

in which R and Y have the meanings given above represents another group of tert-amino-containing alcohols.

Examples to illustrate the alcohols listed above are

HO (CH ₂ ) ₂ NH

■ 0 Γ ~ \

HO (CH ₀ ) _ -NHO

^{Η0 (CH} 2 ^} 3 "~ ^Ν ν ^Η . ^Ν - ^{CH 2 ^} 3 ° ^Η

CH.

Even further classes of alcohols containing tertiary amino groups have the formulas

ho-r !;

or

(4)

HO-R

(5) H0 (R ² ) _k -E

wherein R, Z, E, a, b and k are those given above. meaning

to have. ·

Illustrative examples of such alcohols are 2-, 3- and 4- (2'-hydroxyethyl) pyridine, 3-methyl-4- (2 ^f -hydroxyethyl) pyridine, 2-methyl-4- (2'-hydroxyethyl) pyridine,

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

quinoline and

3-pyridyl-1,5-p entandi oil.

When X in formulas I or II is -NR, a

such group are derived from a primary or secondary amine containing at least one further amino group.

Such amines can be given by the formula (D

where R to R and k have the meaning given above, being represented.

Examples to explain the amines listed above are

(CII ₂ ) ₂ N

- 19 609828 / Ί 043

(CH ₂ J ₈ N (C ₃ H ₇ )

CH, NH (CH_J .N (CH_J _O

O Z H J Z

NH ₀ (CH ₀ J ,, N (C ₀ HJ ₀ Z Zo ZoZ

CH ₃ NH (CH ₂ J ₃ N (CH ₃ J ₂ H ₂ N (CH ₂ J ₂ Ν (CH ₂ CH ₂ OH)

CH ₃ NH-N (CH J

- 20th

6 09828/1043

Another class of primary and secondary amines containing at least one further amino group are heterocyclic ones Connections of the formulas

(2) HN- (R ² ) -NY or

HN H 'NR ⁵
wherein R, R, Rr and Y have the meaning given above.

Illustrative examples of above amines are N- (2 ^f -Aminoäthyl) piperidine, N- (2'-aminoethyl) morpholine, N- (4'-aminobutyl) piperidine, N- (2'-aminoethyl) pyrrolidine, N-methylpiperazine, Piperazine and N- (2-hydroxyethyl) piperazine.

Still other classes of primary and secondary amines containing at least one other amino group are aromatic heterocyclic compounds having five and six membered rings, including
(3). - · / a (4) · 2b '2a.

(5) H ₂ N (R ² ) _k -E

- 21st
6098 28/1043

wherein R, R, Z, E, a and b have the meaning given above

and ν is an integer from 0 to 12.

Illustrative examples of the above mentioned amines are, 2- (2'-aminoethyl) pyridine, 3- (2 ^J -Aminoäthyl) pyridine 2-aminomethylpyridine, 3-aminomethylpyridine, 2,6-dichloro-3-aminomethylpyridine, 2-methyl-3 - (2 '-aminoethyl) pyridine, 3_ (4 ^I- aminobutyl) pyridine, 4-aminomethylpyridine, 4- (2 ^f -aminoethyl) pyridine, 2-aminopyridine, 3-, 4-, 5- or 6-methyl-2 -aminopyridines, 3-, 4-, 5- or 6-chloro-2-aminopyridines, 3-aminopyridines, 2-chloro-6-methyl-3-aminopyridines, 4-aminopyridines, dichloro-4-aminopyridines, 2-aminopyrimidines, 2-, 3- »4-, 5-, 6-, 7- and 8- (4'-aminobutyl) quinolines, 2-, 3-» 4-, 5-, 6-, 7- and 8- (3 «-Methylaminopropyl) quinolines, 2, 3, 4, 5, 6, 7 or 8-aminoquinolines, chloraminoquinolines, methylaminoquinolines, guanine and adenine.

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

R ⁵ A,
where B? and A have the meaning given above.

Suitable compounds of the formula R ⁵ A are those in which R- ^ represents an alkyl group with 1 to 18 carbon atoms and A is any anion which forms an ammonium salt of the formula NH / <3a "with a water solubility of at least 1%. Examples of R ^ A are methyl, ethyl, propyl, isopropyl, butyl, isobutyl,

- 22 -

609828/1043

seki-butyl-, hexyl-, octyl-, Aeth.ylh.exyl-, decyl-, dodecyl-, Tetradecyl, hexadecyl and octadecyl chlorides, bromides and -iodides, benzyl chloride, haloalkanoic acid esters and haloalkyl-alkyl ethers into consideration.

Normal alkyl halides, d. H. n-propyl, n-butyl, n-octyl or n-hexadecyl are preferred. Also come the toluene, benzene and chlorobenzenesulfonate esters of methyl, ethyl, propyl, butyl and similar alcohols as well as methyl and ethyl sulfate in question. When using methyl or Ethyl sulfate (RpSO /) is usually a mixture of RSO * -

and

SO

CIICOOH CH ₂ COX-Q

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

Compounds of the formulas I, II and III, in which Q has the institutes (ic), (2c), (3c), (4c) or (5c), are derived in a similar manner by quaternization with (a) Hal-R ⁶ - COOH

where Hal stands for chlorine, bromine or iodine and R is an alkylene group having 1 to 5 carbon atoms or a group

-CH-

I.
CH ₂ COOH

-C-

I!

CH-COOH

represents

- 23 -

809828/104 3

(b) R ¹⁰ -CHCH ₂ C0 'or

ß-lactones

(c) CH ₂ CH ₂ -SO ₂

CH ₂ 0

Propane sultone

wherein R is hydrogen or an alkyl group having 1 to carbon atoms, from the corresponding amines. The perfluoroalkylthiols used in the preparation of the compounds according to the invention are known to those skilled in the art well known. For example, thiols of the formula RJ1 are -SH in a number of U.S. Patents including 2,894,991 »

2 961 470, 2 965 677, 3 088 849, 3 172 190, 3 544 663 and

3 655 732.

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

R _f -R ¹ -SH

wherein R is alkylenes of 1 to 16 carbon atoms and R ~ is perfluoroalkyl, and taught that halides of the formula R _f -R -hai are well known; Reaction of R ~ J with ethylene under radical conditions gives R ^ (CH ₀ CH ₀ ) J, while reaction of RJDH ₀ J with ethylene RXH ₀ (CH ₀ CH ₀ ) J

JC X c. C- C- SL

as further stated in U.S. Patents 3,088,849, 3,145,222, 2,965,659, and 2,972,638.

U.S. U.S. Patent 3,655,732 also discloses compounds of the formula

R _f -R'-XR "-SH

- 24 609828/10 43

wherein R ¹ and R "denote alkylene having 1 to 16 carbon atoms, the sum of the carbon atoms in R ¹ and R" not exceeding 25; R _f is perfluoroalkyl of 4 to 14 carbon atoms and X is -S- or -NR ¹ ", where R ^! " Is hydrogen or alkyl of 1 to 4 carbon atoms.

U.S. U.S. Patent 3,544,663 teaches that one can use the mercaptan

R _f CH ₂ CH ₂ SH

wherein R "represents perfluoroalkyl with 5 to 13 carbon atoms, by reaction of the perfluoroalkylalkylene iodide with thiourea or by addition of HpS to a perfluoroalkyl- _{substituted ethylene, in turn obtained by dehydrohalogenation of the halide R f} -CH ₂ CH ₂ -hal (R _f -CH = CH ₂ ) can produce.

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

(CF ₃ ) ₂ CF0 CF ₂ CF ₂ (CH ₂ CH ₂ ) _m J.

where m is 1-3 are described in Australian application 36,868 filed April 24, 1968.

Here are thiols of the formula

R _f CH ₂ CH ₂ SH

where R _{£ is} perfluoroalkyl having 6 to 12 carbon atoms, particularly preferred. These R _f thiols can be produced in very large amounts from R ^ CH ₂ CH ₂ J and thiourea.

609828/10

^ F. _CH CH-SH

^C 12 ^F 25 ^CH 2 ^CH 2 ^SH

are illustrative examples of preferred perfluoroalkylalkyl 1 contain oils.

As perfluoroalkylalkylene thiols are

^C 10 ^P 21 ^CH 2 ^CH 2 ^SH

and mixtures thereof are very particularly preferred.

Unsaturated, cyclic dicarboxylic acid anhydrides which can be used in the preparation of the surfactants according to the invention come maleic anhydride as well as alkyl- and halogen-substituted maleic anhydrides such as citraconic anhydride and chloro- and dichloromaleic anhydrides in question. Itaconic and maleic anhydride are preferred, and most particularly Maleic anhydride.

As mentioned above, the compounds according to the invention are effective surfactants and can therefore be used for all surfactants required applications are used. The professional would

6 0 9828 / fo 4 3 ~

these surfactants, of course, as well as prior art surfactants use. The present surfactant is especially useful, for example, as a wetting agent in coatings, waxes, emulsions and Paints applicable. They are particularly valuable as a preparation with other non-fluorinated surfactants Fire-fighting agents. A particular advantage of these surfactants is their low toxicity for those living in water Organisms.

A particular advantage of the compounds according to the invention in which Q has the constitution (la), (2a), (3a), (4a) and (5a) is that it has without the step of using carcinogenic alkylating agents such as β-lactones and amphoteric surfactants which require special quaternization reactions and require propane sultones are. Such a quaternization step is necessary in the case of previously known amphoteric surfactants. Are particularly valuable the compounds according to the invention in the production of aqueous preparations for fire fighting, especially in use in combination with non-fluorinated surfactants. Such. Preparations have superior ones Properties in hydrocarbon fire fighting.

Preferred surfactants according to the invention are the amphoteric surfactants of the formulas Ia and Ha, in which Q has the constitution (la), (2a) or (3a). Are particularly preferred. those in which R _{f is} linear perfluoroalkyl of 6 to 12 carbon atoms, R is ethylene and y is zero. Very particularly preferred surfactants are those in which X is NR

- 27 609828/1 043

and Q corresponds to the constitution (la), where R stands for straight-chain Is alkylene having 2 to 5 carbon atoms and R

-z L

Hydrogen, methyl or ethyl and R ^ and R methyl or Mean ethyl.

It is also well known that one can use mixtures of different types of R "surfactants, such as, for example, nonionic and anion-active R "surfactants, alone or together with common auxiliary hydrocarbon surfactants, such as through Bernett and Zisman (J. Phys. Chem. 6 ^ 5, 448, (1961)) reported that synergistic surface tension effects achieved.

Furthermore, Tuve et al. in U.S. 3,258,423 the use of aqueous solutions of certain R ~ surfactants or R.p surfactant mixtures alone or together with solvents and other additives as effective fire fighting agents. Based on the findings of Tuve et al. are numerous other fire-fighting agents containing various R ^ surfactant systems became known as in U.S. 3,315,325 and 3,772,195.

R - Fire-fighting agents containing surfactants work in two directions:

a. In the form of foams, they are used as primary fire fighting agents.

b. As a dampener, they prevent re-ignition of fuels and solvents.

It is precisely this second property that gives fluorochemical fire-fighting agents their great superiority all other known fire fighting agents.

- 28 609828/1043

Such Rp surfactant fire fighting agents are common known as AFFF (i.e., Aqueous Film Forming Foams). The effect of the AFFF funds comes about because the R "surfactants increase the surface tension Reduce aqueous solutions to such an extent that the solutions are non-polar and water-immiscible solvents wet and spread on, although such solvents are lighter than water; they form a barrier for fuel or solvent vapor, which quickly extinguishes the flames and reignites and reignites be prevented. The criterion necessary to achieve a spontaneous spreading of two immiscible phases is of Harkins et al., J. Am. Chem. 44, 2665 (1922). The measure of the tendency to spontaneous spreading becomes like is defined by the spreading coefficient (SK):

SK = Ya - Tb - Yg where SK = spreading coefficient

Ya = surface tension of the lower liquid phase Yb = surface tension of the upper aqueous phase Yg = interfacial tension between the aqueous phase

upper and lower liquid phase.

If the SK is positive, the surfactant solution should spread and film formation should occur. The higher the SK, the greater the tendency to spread. This requires the lowest possible aqueous surface tension and the lowest interfacial tension, as can be achieved with mixtures of one or more specific R _f surfactants and conventional hydrocarbon surfactants.

609828 / i

mixing achieved.

Commercially available AFFF funds are nowadays mainly used in so-called 6% and 3% safe systems. 6% means that 6 parts of an AFFF agent and 94 parts of water (fresh water, sea water or brackish water) are mixed or dosed and applied at the respective location by means of conventional foam generating devices. In a similar manner, an AFFF agent for the dosage is mixed in such a way that 3 parts of this agent and 97 parts of water are mixed and applied.

AFFF funds are currently being used wherever where there is a risk of fuel or solvent fires and especially where expensive facilities are to be protected. They can be used in a variety of ways, generally hand-held using the usual portable foam nozzles. Hoses, but also according to others Methods such as with Sehwingturm foam nozzles, immersion spraying devices (petroleum tank farms), stationary non-aspirating sprinkler systems (chemical operating zones, refineries), under wing and hangar overflow systems, built into the pipe Dosing systems (induction dosing devices), or aerosol-like dispensing devices, such as those used in the home or in vehicles would apply. AFFF agents are used as fire asphyxiants for class A fires such as wood, textile, paper, Rubber or plastic yours or class B fire like flammable solvent, gasoline, gas or grease fires, especially the latter, recommended. With correct

- 30 609828/1043

Use j on its own or together with dry chemical extinguishing agents (Double systems) they produce a vapor-covering foam with an amazing protective effect.

In general, AFFF agents have set a new benchmark in fuel control and far outperform any previously used protein foams. However, the performance of today's commercial AFFF funds does not yet meet the latest industry demands. The very high price of AFFFs limits their wider application and it is therefore imperative to develop more effective AFFFs that require fewer fluorochemicals to achieve the same effect. Furthermore, it is inevitable that the. To improve minor properties of currently available AFFF funds. The new AFFF products should: a) a lower degree of toxicity (poisoning of fish) is a very important point wherever AFFF products are released in large quantities and where there is the possibility of contamination of receiving waters (rivers and lakes) by such means consists; this is an important problem in test beds where AFFF funds are often used); b) lower chemical oxygen demand (COD) ; good biodegradability (so as not to hinder the activity of microorganisms in biological cleaning systems); c) less corrosive properties so that they can be used in light containers made of aluminum rather than heavy corrosion-resistant alloys; d) improved

- 31 609828/1043

long-term storage stability; e) good compatibility properties with common chemical dry extinguishing agents; f) improved vapor sealing performance and sealing speed; and most importantly, g) have such high performance that they would allow the AFFF agents to be used in 1% dosing systems or below instead of using 3 and 6% dosing systems. This means that 1 part of an AFFF agent can be mixed or diluted with 99 parts of water. The importance of such high performance concentrates is that the storage needs for the AFFF resources would be greatly reduced or, in the case of storage installations, the capacity for available fire fighting agent would be greatly increased. AFFF funds for 1% dosing systems are therefore of great importance wherever storage capacity is limited, such as on coastal oil rigs, coastal nuclear power plants, urban fire engines, etc. The performance expected from an AFFF device today is officially established in most countries (e.g. US Navy MiÜtary Specification MIL-F-24 385 with later additions).

The novel AFFF agents according to the invention described are, compared to today's AFFF funds, not only in terms of the primary performance characteristics, such as the needed time to bring the fire under control, the extinguishing time and the re-ignition resistance, but rather In addition, because of their very high effectiveness, they can also be used in 1% dosing systems. Continue to offer

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they are desirable secondary properties from the standpoint of ecology and economy.

As indicated above, the present invention further relates to aqueous film-forming concentrates for Fire extinguishing or prevention by suppressing the evaporation of flammable liquids, which from

A) 0.5 to 25 wt -.% Of a fluorinated compound (surfactant) one of the formulas I to III,

B) 0.1 to 5% by weight of an anion-active fluorinated surfactant,

C) 0.1 to 25% by weight of an ionogenic non-fluorochemical Surfactants,

D) 0.1 to 40% by weight of a non-ionic non-fluorochemical Surfactants,

E) 0 to 70 wt -.% Solvent and

F) Water to make up the remainder to 100%.

In order to form effective compositions, a mixture of the various surfactants must have surface tensions of achieve less than about 26 dynes / cm. Each component (A) to (E) can consist of a specific compound or of a Mixture of compounds exist.

The above composition is a concentrate which, as stated above, when diluted with water by Formation of a foam, which is deposited as a tough film on the surface of the flammable liquid, its further Prevents evaporation and thus extinguishes the fire, forms a highly effective formulation for fire fighting.

It is a preferred extinguishing agent for fires

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of "flammable solvents, especially for hydrocarbons and polar solvents of low water solubility, especially for:

Hydrocarbon fuels - such as gasoline, heptane ,. Toluene, hexane, aviation fuel, VMP naphtha, cyclohexane, turpentine and benzene;

polar solvents of low water solubility - such as butyl acetate, methyl isobutyl ketone, butanol and ethyl acetate, and polar solvents of high water solubility - such as methanol, acetone, isopropanol, methyl ethyl ketone, ethyl cellosolve and so on.

They can be used simultaneously or one after the other together with flame-suppressing chemical dry powders such as sodium or potassium bicarbonate, ammonium dihydrogen phosphate, COp gas under pressure or Purple K, as in so-called double agent systems. The ratio of chemical dry powder to AFFF agent could be 4.5 to 13.6 kg of chemical dry powder to 7.5 to 37.853 1 AFFF agent in the application concentration (ie after dosing to 0.5%, 1% ₉ 3%, 6 % or 12%). As a typical example, one could use 9 kg of a dry chemical powder and 18.9 liters of AFFF agent. The composition of the invention could also be used in conjunction with hydrolyzed protein or fluoroprotein foams.

The foams of the present invention do not collapse or otherwise detrimentally react with a dry powder such as Purple-K powder (P-K-P).

609828/10

Purple-K powder is the common name for a potassium carbonate fire extinguishing agent, which is flowable and easily forms a powder cloud over flammable liquids and other Lets spread fire.

Normally, the concentrate is diluted with water using a metering system such as a 3% or 6% metering system in which 3 parts and 6 parts of concentrate are mixed with 97 and 94 parts of water, respectively. This highly diluted aqueous composition is then used to extinguish and control the fire.

Component (B) is a fluorinated, anion-active Surfactant. The individual constitution of these surfactants is not critical, and these can be selected from compositions in which the fluoroaliphatic surfactant has one of the formula

where R ~ is a fluorinated, saturated monovalent non-aromatic radical having 3 to 20 carbon atoms, in which the Chain carbon atoms only through fluorine, chlorine or hydrogen atoms with no more than one hydrogen or chlorine atom are substituted on two carbon atoms and in that of a divalent oxygen or trivalent nitrogen atom in the Cferüstkette that is only bound to carbon atoms 0, in which m is the number 0 or 1, for one of alkylene, sulfonamidoalkylene or carbonamidoalkylene radicals existing, polyvalent linking group and Z for a water-solubilizing, polar one consisting of anionic radicals

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Group stands, represents corresponding water-soluble fluoroaliphatic compound.

-CO ₂ "and -SO ~ are preferred as anionic groups. In order to achieve suitable solubility properties, the anion-active surfactant should contain 30-65% fluorine bonded to carbon. The anion-active surfactant can be used as a free acid or its salt with a Alkali metal, ammonium or substituted ammonium are present.

The acids given below and their alkali metal salts are illustrative examples of FU-anion-active surfactants which can be used in the compositions according to the invention. The patent numbers in brackets relate to patent specifications in which the respective class of compounds is disclosed in more detail. Reference is hereby expressly made to these patents. Carboxylic acids and their salts

R ₄ XCOH '(Scholberg et al. J. Phys.

Chem. 57, 923-5 (А953)

' ^R £ ^iCH 2'l-20 ^COOH ( ^{DT λ 91β 669} ^

R _f O (CF ₂ ) ₂ _ _2Ü COOH (DT 2 132 164)

R _f O (CF ₂ ) ₂ _ ₂₀ (CH ₂ ) ₂ _ ₂₀ COOH (DT 2 132 164)

^R f ^{O (CH} 2 ^{) 1-20 COOH} "(US 3 409 647) N (C ₂ H ₅ ) CH ₂ COOH (US 3 258 423)

(F 1 531 902) CF ₂ COOH (F 1 537 922)

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R 0 [CF (CF) CF O] CF (CF-) CON (CH ₀ ) CH ₀ COOH

(US 3 798 265)

(C ₂ F ₅ J ₂ (CF ₃ ) CCH ₂ COOH '(GB 1 176 493)

^C 10 ^F 19 ^OC 6 ^H 4 ^CONiCH 3 ^{) CH} 2 ^COOli ^ ^{GB λ 27} ° ⁶⁶² ^

R _f (CH ₂ J _1-3 SCH (COOh) CII ₂ COOH. (US 3,706,787)

R- (CH ₀ ). . "S (CH ₀ J _1. -COOII (DT 2 239 709;
f 2 1-12 2 1-17 _us 3 ₁₇₂ 90O

Sulfonic acids and their salts

R _f SO ₃ H (US 3,475,333)

R, C, H, SO, H (DT 2 I34 973)

Rf (CH ₂ J _1-20 SO ₃ H (DT 2 309 365)

R-SO ₀ NHCH _n C Al, SO_H (DT 2 315 326)

^R f ^SO 2 ^{N (CH} 3 ^{) CC} 2 ^H 4 ^O) l-20 ^SO 3 ^H (South-Afr. 693 583)

R _f CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ SO ₃ H (Kan. 842 252)

. R _f OC ₆ H ₄ SO ₃ H '(DT 2 23Ο 366)

C ₁₂ F ₂₃ OC ₆ H ₄ SO ₃ H (DT 2 240 263)

(C ₂ F ₅ J ₃ CO (CH ₂ ) ₃ SO ₃ H (GB 1 153 854)

CF ₃ (C ₂ F ₅ J ₂ CO (CH ₂ J ₃ SO ₃ H (GB 1 153 854)

(C ₂ F ₅ J ₂ (CF ₃ ) CCH-C (CF ₃ ) SO ₃ H (GB 1 206 596)

R _f OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) COiJHCH ₂ SO ₃ H (US 3 798 265)

Phosphonates, phosphates and related phosphorus derivatives

and their salts

"R _f PO (OH) ₂ (R _f ) ₂ PO (OH) · (DT 2 110 767)

R ₄ -SO ₀ N (Et) C ₀ H-OPO (OHJ ₀ (DT 2 125 836)

R _f CH ₂ OPO (OH) - (DT 2 I58 66I)

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^C 8 ^F 15 ^0C 6 ^H 4 ^CH 2 ^{P0 (0H)} 2 (DT 2 215 387)

R _f 0C ₆ H ₄ CH ₂ P0 (QH) ₂ (DT 2 2 ^ 0 366)

Other (and their salts)

R _f SO ₂ N (CH ₃ ) C ₂ H ₄ OSO ₃ H (DT 1 621 107)

R _f C ₅ H ₄ OH ■ (US 3 475 333)

^R f ^(CH 2 ⁾ l-20 ^S 2 ° 3 ^Na '(DT 2 115 139)

(DT 2 115 139)

R _f S0 ₂ H (US 3 562 156)

The reaction of 1,3-propane sultone with a Perfluoroalkylthiol of the formula

R _f -Ri-S- (CH ₂ J ₃ SO ₃ Z

where R- and Z are those given above and R are those given below Have meaning, the type of compound formed is particularly preferred as the fluorinated anion-active surfactant of the sulfonate class.

The perfluoroalkylthiols used in the manufacture of the sultones are well known in the art. For example, thiols of the formula RJl -SH are in numerous " U.S. Patents including 2,894,991, 2,961,470, 2,965,677.3,088,849, 3,172,190.3,544,663, and 3,655,732.

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

wherein R is alkylene of 1 to 16 carbon atoms and Γ is perfluoroalkyl, and teaches that halides of the formula Rf-R -hai are well known; Implementation of R _f J with

- 38 6 09828/104 3

Ethylene under radical conditions gives R- (CH ₂ CH ₂ ) J,

during ■ implementation of R _f CHpJ with ethylene

R _f CHp (CHpCH ₂ ) J leads as continued in US patents

3,088,849, 3,145,222, 2,965,659, and 2,972,638

U.S. U.S. Patent 3,655,732 also describes Verbiradungender formula

R ^ -R ^3- -XR "-SH

wherein R and R "for alkylene with 1 to 16 carbon atoms, the sum of the carbon atoms in R and R" does not exceed 25, R _f for, perfluoroalkyl with 4 to 14 carbon atoms and X for -S- or -NR ¹ "- where R " ¹ is hydrogen or alkyl having 1 to 4 carbon atoms.

The preferred synthetic route for the preparation of the mercaptan R ~ -R -SH is the implementation of the iodide R ~ -R -J with thiourea with subsequent hydrolysis. The response is to both linear and branched chain iodides applicable. Numerous valuable perfluoroalkoxyalkyl iodides the general formula

(CF ₃ ) ₂ CF0 CF ₂ CF ₂ (CH ₂ CH ₂ ) _ffi J where m is 1-3 are described in U.S. Patent 3,514,487.

Below are the thiols of the formula

R _f CH ₂ CH ₂ SH

where R _{f is} perfluoroalkyl having 6 to 12 carbon atoms, particularly preferred. These R _f thiols can be prepared in very high yield from R ^ CH ₂ CH ₂ J and thiourea.

09828/10 ^ 1 "

Component (C) as an ionic, non-fluorochemical, water-soluble surfactant is selected from among anion-active, cation-active or amphoteric surfactants, as described in Rosen et al ., Systematic Analysis of Surface-Active Agents , Wiley-Interscience, New York (2nd edition, 1972), pages 485-544, lists to be found, which are hereby expressly referred to, reproduced.

It is particularly useful to use amphoteric or anion-active fluorine-free surfactants, since these over against the Effects of the fluoroaliphatic surfactant structure or opposite relatively insensitive to the ion concentration in the aqueous solution and also in a broad range relative solubilities are available, which facilitates the selection of suitable materials.

The main point of view in choosing more preferred ionogenic non-fluorochemical surfactants is that they have an interfacial tension below 5 dynes / cm at concentrations of 0.01-0.3% by weight. You should continue high degrees of foaming at their use concentrations have, at application and storage temperatures occurring in practice, heat-stable, acid- and alkali-resistant, biological Easily degradable, especially non-toxic for organisms living in water, easily dispersible in water, against hard or sea water must be insensitive and compatible with anion-active or cation-active systems, protective coatings Form on materials, pH-insensitive as well as commercially available and

- 40 - '

Ö09828 / 1043

to be cheap.

According to the classification scheme to be found in Schwartz et al., Surface Active Agents , Wiley-Interscience, NY, 1963, which is hereby expressly referred to, anion-active and cation-active "lenses" are firstly classified according to the type of their solubilizing or hydrophilic group and second, according to the way in which the hydrophilic and hydrophobic groups are bonded, ie directly or indirectly, and if indirectly, according to the type of bond.

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

Typical anion-active surfactants include carboxylic acids, sulfuric acid esters, alkanesulfonic acids, alkylaromatic ones -Sulfonic acids and compounds with other anionic hydrophilic Functions such as phosphates and phosphonic acids, thiosulfates, sulfinic acids, etc.

Because of their hydrolytic stability and easy accessibility, carboxylic or sulfonic acids are preferred. Illustrative examples of anion-active surfactants are:

C ₁₂ H ₂₅ OSO ₃ Na
Alkyl diphenyl ether disulfonate disodium salt

/ • 1 _

609828/1043

Q η Q SL 0 »/ 1 Π L 'S

Sulfosuccinic acid half-ester disodium salt derived from an ethoxylated C-, q-, ₂ -alcohol, sodium alpha-olefin sulfonate) C ₂ H ₄ SO ₃ Na

C ₁₁ H ₂₃ CON (CH ₃ ) CH ₂ CO ₂ Na

Typical cation-active classes include amine salts, quaternary ammonium compounds and other nitrogen-containing and nitrogen-free bases, e.g. B. phosphonium, sulfonium and sulfoxonium; also the special case of amine oxides, which are known to be cationic under acidic conditions can view.

For reasons of stability and easy accessibility, preference is given to amine salts, quaternary ammonium compounds and other nitrogen bases. In view of corrosion, cation-active compounds not containing halide are preferred. Illustrative examples of cation-active surfactants are: Bi s (2-hydroxyethyl) tallow amine oxide hydrogenated dimethyl tallow amine oxide is ο stearylimldazollnlumethosulfate coco sylimidazolinium ethosulphate lauroylimidazolinium ethosulphate [C ₁₂ H ₂₅ OCH ₂ CH (CH) _{2 CH 2 CH} (CH ₃ ) CH ₂ CH ₂ OH) ₂ ] +

CH ^ SO, ~

[C ₁₇ H ₃₅ CONH (CH ₂ ) N (CH) ₂ CH ₂ CH ₂ OH] NO ₃ -

- 42 6098 2-8 / 1043

Amphoteric non-fluorochemical surfactants include compounds which, in the same molecule, have the following Groups contain: amino and carboxyl, amino and sulfuric acid esters, amino and alkanesulphonic acids, amino and aromatic Sulphonic acid and various combinations of basic and acidic groups, as well as the special case of aminimides.

Preferred are those non-fluorochemical amphoteric compounds which are amino and carboxyl or Contain sulfo groups, as well as the aminimides.

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

Or ¹ -O l ς ^M - + / ο * "- + / * / * ^{R (H}} n ** ^C " ^N ~ \ ~ ^{R or} R (H) _n -CNN-CHR ₄ -C OH

Sulfonylaminimides of the general formulas:

R (H) SO NNR or R (H) SO ₀ NN-CHR -C-OH

V. · V V

Aminocyanimides, aminonitroimides or functionally substituted Aminimides, as described in U.S. 3,499,032, U.S. 3 485 806 and GB 1 181 218, which are hereby expressly referred to is described.

Among the above-mentioned aminimides, preferred are

6098287

25531.83

especially the carboxaminimides because of the combination the extremely desirable surface-active properties listed below:

a) they "are high surface active and have low Concentrations of very low interfacial tensions and therefore produce films with an extremely high spreading coefficient;

b) they are amphoteric and therefore with any type of fluorosurfactant - ■ anion-active, cation-active. Non-ionogenic or amphoteric - compatible;

c) they are heat-stable at application and storage temperatures occurring in practice;

d) they are acid and alkali resistant;

e) they are biodegradable and non-toxic;

f) they are easily dispersible in water;

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

h) they are cheap and commercially available.

Illustrative examples of non-fluorochemical amphoteric surfactants are: coconut fatty _{betaine (CO 2} ") coconut oil amidoethylhydroxyethylcarboxymethylglycine betaine coconut amidoammonium sulfonic acid betaine cetyl betaine (type C)
A sulfonic acid betaine derivative

C ₁₃ H ₂₇ CONN (CH ₃ ) ₂ CH ₂ CH 0 HCH

- 44 609828/1043

2559139

₂₇
C ₁₅ H ₃₁ CONN (CH ₃ )

MN (CH ₃ ) ₂ CH ₂ CHOKCH ₃ NIJ (CH ₃ ) ₂ CH ₂ CHOHCH ₃ IW (CH ₃ ) 3
(CH ₃ ) 3

H CK OCH CO, Jv ' ^{2 2 2 2}

'- XILCO ^ Na 2 2

A coconut derivative of the above coconut betaine

^C 12 -14 ^H 25-29 ^te 2 ^CH 2 ^CH 2 ^C00 "(triethanolammonium salt)

+ / CHXILCO-- ^ 2 2 2

The non-ionic, non-fluorochemical surfactant component. (D) is used in the aqueous fire fighting compositions mainly as a stabilizer and solubilizer, for the compositions, especially when diluted with hard or sea water, incorporated. The non-ionic compounds are chosen mainly on the basis of them hydrolytic and chemical stability, solubilizing and emulsifying properties (e.g. according to HLB values, hydrophilic / lipophilic balance) »cloud point at high salt concentrations, toxicity and behavior at biodegradation. Secondly, the selection is made in

- 45 609828/1043

With regard to the degree of expansion, the foam viscosity, foam drainage, surface tension, interfacial tension and network properties.

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

Polyoxyethylene derivatives of alkylphenols are preferred, linear or branched alcohols and glucosides as well as block polymers of polyoxyethylene and polyoxypropylene, the first two mentioned are very particularly preferred.

Illustrative examples of non-ionic, non-fluorochemical surfactants are:

Octylphenol (EO) _{g 1Q} (EO) ₁₅

Nonylphenol (EO) g ■

Lauryl ether
Stearyl ether
Sorbitan monolaurate (EO) p ₀

- 46 -609828/1043

Dodecyl mercaptan (EO) -, q block copolymer from (EO) (PO). C ₁₁ H ₂₃ CON (C ₂ H ₄ OH) ₂

25th

XCH ₂ CH ₂ O) ₇ H χ + y = 25

NOTE: EO or PO as used above mean recurring ethylene or propylene oxide units. The component (E) is a solvent which is used as

Antifreeze or foam stabilizer acts or acts as a refractive index modifier, so that the dosing systems can be calibrated under practical conditions.

This is not really an indispensable part of the invention Composition because highly effective AFFF concentrates can be obtained in the absence of a solvent. Rather, it is one of the unexpected and unusual features of this invention as compositions are known in the art usually require the use of a relatively high percentage of solvent. However, it is also with the Compositions according to the invention often advantageous to use a solvent, especially when the AFFF concentrate is to be stored at freezing temperatures. Useful solvents are disclosed in U.S. Patents 3,457,172, 3,422,011 and 3,579,446 and German patent 2,137,711.

Typical solvents are alcohols and ethers such as ethylene glycol monoalkyl ethers, diethylene glycol monoalkyl ethers,

609828/1043 - 47 -

_{Propyienglykolmonoalkylather}} Dipropylenglykolmonoalkyläther, Triäthylenglykolmonoalkyläther, l-butoxyethoxy-2-propanol, Glyzerinj Diäthylcarbitol, Hexylenglykolj 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.

l-butoxyethoxy-2-propanol, diethylene glycol monobutyl ether or hexylene glycol are preferred solvents.

Other components that may be present in the formulation are:

- Buffers of a largely unrestricted type, for example Sörensen's phosphate or Mcllvaines citiate buffer.

- Corrosion inhibitors of an unlimited nature as long as they are compatible with the other components of the formulation.

- Unrestricted chelating agents, for example polyaminopolycarboxylic acids, ethylenediaminetetraacetic acid, citric acid, gluconic acid, tartaric acid, nitrilotriacetic acid and hydroxyethylethylenediamine triacetic acid, and their salts t

- High molecular foam stabilizers such as polyethylene glycol, hydroxypropyl cellulose or polyvinylpyrrolidone.

The concentrates of the invention are with everyone Fire-fighting assemblies with effective pH value, however, are provided generally such concentrates with dilute acid or alkali to a pH of 6 to 9 »and particularly preferably a pH of 7 to 8.5. Organic acids can do this

- 48 -

6 09828/1043

559189

or mineral acids such as acetic acid, oxalic acid, sulfuric acid, phosphoric acid etc., or metal hydroxides or amines, such as sodium or potassium hydroxide, triethanolamine, tetramethylammonium hydroxide etc., can be used.

As mentioned above, the compositions according to the invention are concentrates which must be diluted with water before use as a fire-fighting agent. Although due to the availability of fire extinguishers which can automatically mix the concentrate with water in such proportions, currently the most practical and therefore preferred concentrations of said composition in water are 3% and 6% , there is no reason why the concentrate should not be used in lower concentrations from 0.5% to 3% or in higher concentrations from 6% to 12%. This is only a question of the expediency, the type of fire and the effectiveness desired for extinguishing the flames.

A very useful AFFF concentrate composition for a 6% dispensing system consists

A) 1.0 to 3 »5% by weight of amphoteric fluorinated surfactant,

B) 0.1 to 2.5% by weight of anion-active fluorinated surfactant,

C) 0.1 to 4.0 wt -.% Non-ionic fluorochemical surfactant,

D) 0.1 to 8.0 wt -.% Of non-ionic non-fluorochemical surfactant and

E) 0 to 20% by weight solvent and enough water to make up the remainder to 100%.

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609828/1043

The present composition can also be easily dispensed from an aerosol-type container using a conventional inert propellants such as Freon 11 »12 or 22 or NpO, Np or air. Expansion volumes up to a height of 50, based on the air / liquid ratio, can be achieved.

The amphoteric R ~ surfactants of component (A) are the most important elements in this novel AFFF system.

These R ,, amphoteric surfactants reduce the surface tension of the aqueous solutions to about 20 dynes / cm and act as solubilizers for the R ^ surfactants of type B, which contribute to the majority of the excellent properties of the novel AFFF agents according to the invention. The anion-active R surfactants of component (B) act as a surface tension reducer for the amphoteric surfactant of component (A) (synergistic R - surfactant mixtures), which reduce the surface tension to 15-16 dynes / cm and usually in much lower concentration than that Rp surfactants of component (A) are present. Furthermore, the R ~ surfactants of component (B) increase the spreading speed of the aqueous AFFF films on hydrocarbon fuel en and make an important contribution to the excellent Resealability of the novel AFFF agent. The ionic or amphoteric hydrocarbon surfactants of component (C) fulfill a double function. They act as interfacial tension reducers by reducing the Interfacial tension of the components (A) and (B) as R -, -

- 50 609828/1043

Aqueous R ~ surfactant solution containing surfactants can be reduced from interfacial tensions of up to 10 dynes / cm to as low as 0.1 dynes / cm. Furthermore, the auxiliary surfactants of component (C) act as foaming agents , and the degree of foaming of the novel AFFF agent can be varied by changing the amount and proportions of the auxiliary surfactants of component (C). The non-ionic hydrocarbon surfactants of component (D) in the new AFFF agent also have multiple functions in that they act as solubilizers for the R ~ surfactants of components (A) and (B) with poor solubility properties. Furthermore, they have stabilizer effects, especially for AFFF agents / seawater premixes and also influence the shower stability of the AFFF agent and, as explained below, the foam drainage time. They also have an influence on the viscosity of the AFFF agents, which is particularly critical in the case of 1% dosing systems. The solvents of component (E) are used in a similar way as solubilizers for R «surfactants, but they also act as foam stabilizers, serve as refractive index modifiers to calibrate the dosage under practical conditions, reduce the viscosity of highly concentrated AFFF agents and act as antifreeze agents. Whereas commercially available AFFF agents for 6% dosage have high solvent contents of over 20%, this invention teaches the production of comparable preparations with excellent performance at solvent contents of up to

- 51 609828/1043

25591 ^ 9

3? & Go down.

Some of the solvents present in the AFFF preparations are only present because they are introduced into the product _{by the R f surfactant synthesis.} In addition to the contributions that the components listed so far can make to the behavior of the new AFFF agent, it should also be mentioned that these candidates were also selected because of their very low toxicity, as shown in the experimental part of this application. As already mentioned, other additives to your novel AFFF remedy can be beneficial, such as:

Corrosion inhibitors (for example in the event that aqueous AFFF premixes are stored in uncoated aluminum cans for several years).

Chelating agents (when premixes of AFFF agents and very hard water are stored for long periods of time). Buffer systems (if a certain pH value has to be maintained for a longer period of time).

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

Polymeric thickening agents (if, due to certain requirements of the dosing system, higher viscosities of the AFFF agent / water premixes are desired), and. .so on.

Today's commercially available AFFF agents can only be used in 6 and 3% dosing systems. The composition of the present AFFF agents and the quantity ranges of the various active ingredients of this novel AFFF-

- 52 60 9 8 28/1043

The mean is expressed for 0.5 to 12? S metering systems. Doubled one the concentration of a composition for 6% dosage, then one can use such a concentrate for one Use the 3? & Dosing system. With a 6-fold increase in Concentration of such a 6% dosing system can then be used Use similarly as a l $ i dosing system. Like comparison values in the experimental part show that the preparation of such 1% dosing systems is mainly possible because

A. because the new R ~ surfactants used have a higher Have effectiveness and therefore require smaller amounts;

B. because those required in the new AFFF funds, rather low levels of solvent can achieve the expansion ratios required by the military.

The examples refer to the specifications valid in industry and especially in the military our own tests to assess the effectiveness of the claimed compositions. More in detail the examples relate to the following specifications: Surface and Interfacial Tension - ASTM D-1331-56 Freezing Point - ASTM D-1177-65

pH - ASTM D-1172

Testing the sealability

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

- 53 609828/1043

Procedure : Ten ml of cyclohexane are pipetted into a 48 mm evaporation dish in an Evaporometerktvette. Helium flowing at 1,000 cc per minute flushes the cyclohexane vapors out of the cuvette through a 3 cm IR gas cell attached to a PE 257 infrared spectrophotometer (registered infrared spectrophotometer). The IR extinction of the gas stream in the area of 2,850 cm -1 is continuously monitored while solutions of the preparations are poured onto the surface. The infusion. The preparations on the cyclohexane surface are done at a rate of 0.17 ml per minute using a 1 cc tuberculin syringe driven by a syringe pump with a 13 cm long, number 22 needle, the needle just touching the cyclohexane surface.

The syringe pump is switched on as soon as the extinction for "unsealed" cyclohexane has been set. The moment when the very first drop of the formulation solution hits the surface represents the time zero. The time for 50% sealing and the percent sealing after 30 seconds and after 2 minutes are recorded. The time for 50% sealing is closely related to the rate of film expansion (see below), and the percent sealing after 30 seconds and 2 minutes is closely related to the effectiveness and performance of the film as a vapor barrier.
Checking the speed of film propagation

Objective : To determine the speed with which an AFFF film spreads over a cyclohexane surface.

- 54 609828/1043

2 5 5

Procedure ; A 6 cm aluminum dish is half-filled with cyclohexane, and a 50 μΐ syringe is filled with a 6% solution of the test solution. 50 μΐ of the solution are sprayed down the wall of the dish as quickly and carefully as possible so that the solution flows gently onto the cyclohexane surface. Cover the dish with an inverted Petri dish and start a stopwatch at the end of the injection. The spread of the film over the surface is observed and the stopwatch is stopped at the moment when the film completely covers the surface and the elapsed time is noted.
Match test

Objective : To approximate the sealability of an AFFF film.

Procedure : An aluminum weighing pan (58 15 mm) is filled two-thirds full with cyclohexane per analysi. About 2 ml of the AFFF solution to be tested is carefully poured onto the surface. You light a wooden match, and when the initial flare of the match has subsided, you quickly dip the flame through the sealed surface and then pull it back out of the bowl. The flame will go out. Repeat this with more matches until you achieve sustained ignition and note the number of matches used.
Fire tests

The most critical test for the present composite

- 55 609828/10 43

Settlement consists in practical fire tests. The single

p hexes the procedure for such tests at 2.60 m -,

ρ ρ

4,647 m and 117.0 m fires are in U.S. Navy Specification MIL-F-24385 and its additions indicated.

Procedure ; Vorini loops of the compositions according to the invention are produced from 0.5 to 12% dosage concentrates and tap or sea water, or the AFFF agent is dosed using a metering system built into the pipe. In each case, the test preparation is used in the appropriate concentration for use.

The effectiveness of the compositions according to the invention to extinguish hydrocarbon fires

repeated and reproducible on 2.60 m gasoline fires as well as on a circular disc with a 12.19 m diameter

listed 117.0 m firing proved. The tests were often carried out under severe environmental conditions with wind speeds up to 16 km per hour and with prevailing summer temperatures up to 35 ° C. All exams of the Performance on fire as well as additional tests foaming capacity, film formation, sealing ability, film spreading speed, Viscosity, drainage time, spreading coefficient and stability - confirmed that the Compositions of the invention performed better than that Prior Art AFFF Compositions.

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

1. Checkout Time - The time required to finish the fire

- 56 609828/1043

To bring the fire fighting agent under control or to master it.

2. Extinguishing Time - The time from the start of application until the fire is completely extinguished.

3. Reignition Time - The time of the total Extinguish the flame until the hydrocarbon liquid reignites when applying an open flame to the surface.

4. Addition of % fire extinguishing - When extinguishing

When firing 4.645 or 117.05 m, the total is recorded the percent fire extinguished values at 10, 20, 30 and 40 second intervals »The current prescription for 15,000 feet — Fire requires a "total" of 225 or

larger, and for 117 »O5 m —fires of 285 or larger.

2.60 m; - fire test

This test was carried out in a flat round pan with a diameter of 1.83 m made from 0.635 cm thick steel (2.60 square meters) with sides that are 12.70 cm high, giving approximately 6.35 cm of freeboard during testing. To keep gasoline on a water substrate, she had Pan no outlets. A minimum water depth was maintained and only served to completely cover the pan to ensure with fuel. The nozzle for applying the agent provided a flow rate of 7.57

per minute at 7> 03 kg / cm pressure * The outlet was through modified a "wing tip" manifold with a 3.175 mm wide, 4.76 cm long circular arc opening.

- 57 -

b09828 / lü43

The premix solution in fresh water or sea water was at 21 ⁰ C - 5> 5 ° C. The extinguishing agent consisted of a 6 percent dosage concentrate or an equivalent amount in freshwater or seawater and the fuel load was 37 »85 liters of gasoline. The entire load of fuel was poured into the diked area over 60 seconds, and the fuel was ignited within 60 seconds of the end of fuel injection and allowed to burn freely for 15 seconds before the extinguishing agent was applied. The fire was extinguished as quickly as possible by holding the nozzle at an angle of 1.07 to 1.22 meters upwards from the floor, at a distance such that the nearest edge of the foam mold could fall on the nearest edge of the fire. After the fire was extinguished, the extinguishing time was noted, continuing to distribute the agent over the test area until exactly 11.36 premix had been applied (90 second application time).

The flame retardancy test was completed within 30 Started seconds after the 90-second application of the solution. A weighted, 0.946 liter of gasoline was placed 30.48 cm diameter pan with 5 »08 cm sidewalls in the center of the area. The fuel in the pan was ignited just before setting. The reignition time started at the moment of this setting and ended when 25 pro

2
cent (0.65m) of the originally foam-covered

Fuel surface burned. As the large test pan area Flaming entertained, the small pan was removed.

- 58 -

6 0 9 8 2 8/1043

117, Om ² - fire test

This test was carried out on a flat, circular surface (117.0 m ² ).

The water depth was the minimum required to completely cover the diked area with fuel to ensure. The nozzle used to apply the agent was designed to deliver 189.27 liters per minute at 7.07 kg /

cm.

The solution in fresh or sea water had a temperature of 20 ⁰ C - 5.50 ° C and contained 6.0 - 0.1% of the composition of the invention. The fuel consisted of 1,135.6 liters of gasoline. No tests were carried out above wind speeds of 16 km per hour. The entire load of fuel was poured into the diked area as quickly as possible. Before the fuel was introduced for a test, all extinguishing agents from the previous test were removed from the diked area.

Within 2 minutes after the end of the introduction of the fuel, the latter was ignited and before the application of the Let extinguishing agent burn freely for 15 seconds.

The fire was extinguished as quickly as possible by placing the nozzle 1.07 to 1.22 m above the ground inclined upwards at such a distance that the nearest edge of the foam mold was on top of the nearest Edge of the fire could fall.

At least 85 percent of the fire was within

- 59 609828/1043

30 seconds to extinguish, and the "percent fire extinguished" values were noted.

example 1

N-Γ3- (Dimethylamine ») propyl] -2- or -3- (l, l, 2,2-tetrahydroperfluorodecylthio ) suecinamic acid

CH ₂ COKH (CH ₂ ) ₃ NH (CH ₃ ) ₂ or

UH (CH ₃ )

Maleic anhydride (10.0 g; 0.102 mol) and a mixture of ethylene glycol dimethyl ether (100 g) and NjN-dimethylformamide (60 g) in a stirred, under nitrogen reaction flask kept and cooled to 10 ° C. in an ice bath. In the course of half an hour, 3-dimethylaminopropylamine becomes (10.4 g; 0.102 mol) was added dropwise at a reaction temperature of 10-15 ° C. The resulting white is stirred Suspension for one hour at room temperature.

A small amount of this product is dried, washed with heptane and dried for 12 hours at 3O ⁰ C in vacuo. The infrared analysis and NMR signals characterize a connection of the constitution:

- 60 6 09828/1043

HC

Il

HC ©

^ CONH- (CH ₂ ) ₃ N (CH ₃ ) ₂

N- (3 ~ dimethylaminopropyl) maleic acid amide.

1,1,2,2-tetrahydroperfluorodecyl mercaptan (49.0 g; 0.102 mol) is added all at once and the resulting mixture is stirred Mix at room temperature for 64 hours. The thick suspension is filtered and the solids with acetone washed and then dried at room temperature under vacuum (0.1 torr) for 18 hours. The product is obtained as a white powder weighing 61.2 g (yield = 88.2? o) and Melting point 123-128 ° with slow decomposition (gas evolution) above the melt. The infrared spectrum is right with the constitution, in particular the amide band at 1660 cm ~ in the solid phase and at 1660 cm "" in the dilute phase Chloroform solution, as well as the asymmetrical or symmetrical carboxylate elongation bands at 1550 cm * "or 1320 to 1390 cm" The NMR spectrum is in agreement with the constitution and gives the following signals:

2.68 ppm N-CH; 1.8-2.1 NCH ₀ CH ₀ CK ₀ N j - · * * ά. £

"I "

The surface tension (γ) of the aqueous solution

- 61 -

ÜO9828 / 1043

of the above compound is 19.8 dynes / cm. In this and the following examples are surface tension measured at a concentration of 0.1% in water at 25 ° C with a Du Nouy tensiometer.

Example 2

N-Γ3- (Dimethylamine) propyl1 ~ 2- or -3- (l, l> 2,2-tetrahydropic fluoroalkylthio ) succinamic acid

IUCH ,, CH-SCHCOO-

ι Q *

CII ₉ CONH (CII ₀ ) 'NH (CH-) _o

asfie their isomer

The mixture is stirred maleic anhydride (IQO g; 1.02 mol) and N-methylpyrrolidone (400 g) under inert gas in an in ice / salt geraisch to ⁰ ° C cooled reaction flask and admixed dropwise at 0-1O ⁰ C for 40 minutes in N-methylpyrrolidone (100 g) dissolved 3-dimethylaminopropylamine (106 g; 1.04 mol). The dark brown suspension is stirred for 20 minutes at room temperature and then mixed with methanol (800 g), whereupon the resulting low-viscosity suspension is heated to 45.degree. 1,1,2,2-Tetrahydroperfluoroalkylmercaptan (483 g; 0.94 mol) (Geraisch of compounds with different alkyl groups as follows: Cg-25%; Cg-50% and C ₁₀ -25%) is within 10 minutes at 45 -50 C was added, resulting in an amber-colored solution, which was stirred at 45 ° C for 3 hours. The completeness of the reaction is due to the disappearance of the perfluoroalkylethyl mercaptans

- 62 -

6 0 9 8 2 8/1043

Gas chromatography demonstrated trace amounts in the reaction mixture. The identity of the product is confirmed by the infrared absorption for the amide function at 1655 cm * ", and carboxylate shows up at 1560 cm - and 1325-1400 cm ". Gas chromatography reveals three perfluoroalkyl acid areas, two solvent areas and the mercaptans attributable trace areas. The obtained NMR proton signals ■ are essentially identical to those from Example 1. The compound melts at 95 ° to 115 ° C. the The surface tension of the aqueous solution of said compound is 17.7 dynes / cm.

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

- 63 609828/1 0A3

Example _:. No. R _f -thiol

CD O CO OO

3 1 v «#>^< *** f * 7 ^s ^ '\ r ^A

CH,

Cation-active
link Y ₀ (dyn / cm) ^ - ^CH 3 20.6 H ₀ NN
. ² \
CH ₃ / ^C 2 ^H 5 17.3 2 2 ^λ · _Ν
C ₂ H ₅ CK, 20.4 I ₂ CH ₂ CH ₂ -N. ^CH 3

C ₈ F ₁₇ C ₂ K ₄ SH • _{/ C} H ₂ -CH 19.4

K ₀ N-CH ₀ CH ₀ CH ₀ -N 0

CH ₀ -CH ₀ '2 2

₀ CH ₀ 2 2

3 '17.9 .--

H ₀ N-CH ₀ CH ₀ -N CO

CH ₃ .

Example 8

N-methyl "N- (2 ^I -N ^l _> N ^l -dimethylaminoethyl) -2- or -3- (l> l, 2 tetrahydroperfluoroalkylthio) succinamic acid

R CH CH S-CHCOO ^

1/7 \ ^ r 3

• ^ / and isomer

CH ₀ CON-CiI ₀ CH ₀ NH

² I ²² X

R _f is a mixture of C ^ F ^ (25%), CgF ₁₇ (50%) and C ₁₀ F ₂₁ (25%).

Powdered maleic anhydride (0.033 mol, 3 * 24 g) is added in portions to a cooled solution of (N, N ^f , N ^t -trimethyl) -ethylene-1,2-diamine (0.033 mol, 3.47 g) in 6, 7 g of water. The reaction is carried out under nitrogen and held by means of an ice bath at 10-20 ⁰ C. When the addition is complete, the bath is removed and the reaction mixture is stirred for 1-2 hours at room temperature.

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

■ ^B 3 ^C \ © / ^CH 3

N
I c;

mark. Titratable acidic hydrogen is not available.

CH

- 65 609828/1043

The light yellow solution is mixed with 2-methyl-2,4-pentanediol (20.13 g) and then with perfluoroalkylethyl mercaptan (0.3135 mol, 14.65 g). The resulting white
^{The suspension is heated to 90 °} C. with stirring until the reaction is complete (6.5 hours). The clear, pale yellow solution is cooled to room temperature and diluted with water
(23 g) on 30% solids. The cloudy solution is filtered clear (asbestos wad with 5 μ porosity) and gives 66.5 g (93 1 4%) of a clear, light yellow solution. Infrared analysis is consistent with the constitution. The surface tension (γ) of the aqueous solution of the above compound is 18.3 diyne / cm.

Example 9

After the above procedure is prepared from maleic anhydride, R _f C ₂ H ₄ SH and N, N-dimethyl-N'-ethyl-ethylene-l, 2-diamine, the compound N-ethyl-N- (2 ^t -N'N -dimethylaminoethyl) - Z- or -3- (l>l> 2,2-tetrahydroperfluoroalkylthio) succinamic acid. The surface tension of this connection
is 20.2 dynes / cm.

Example 10

N- (2-dimethylaminoethyl) -2- or -3- (l> l »2,2-tetrahydroper fluoroalkylthio) suecinamic acid

R ^ CH ^ CH ^ S-CHCOO ^

■ © / 3 and isomer

j [iIICII "CH - N-K

k ^{2 2} \

Powdered maleic anhydride (0.033 mol,

609828/1043

- 66 104 '

3.24 g) in portions to the cooled solution of (N, N-dimethyl) -ethylene-1,2-diamine (0.033 mol, 2.90 g) in 6.7 g of water. The reaction is carried out under nitrogen and maintained at 10-2O ⁰ C by ice "bad". When the addition is complete, the bath is removed, the reaction mixture is stirred overnight at room temperature and 2-methyl-2,4-pentanediol (20.13 g) and then perfluoroalkylethylmercaptan (0.3135 mol, 14.65 g) are added to the light yellow solution ). To complete the process (6.5 hours), the resulting white suspension is heated ^{to 30 ° C. with stirring.} Cool the light yellow solution to room temperature and dilute to 30% solids with water. It is filtered clear through an asbestos wad with 5 μ porosity and 66.5 g (93.4%) of a clear, light yellow solution are obtained. The surface tension of the aqueous solution of the above compound is 22.0 dynes / cm.

According to the procedure described above, compounds analogous to Example 10 are prepared from maleic anhydride and the starting materials given below:

- 67 6 09828/1043

Example no.

R ^ thiol

-Cation-active
link

Y ₀ ctyn / cm

11

C ₂ H ₅

21.3

cn
CJ I. 3828 / cn
. co ο -P-
OO

12th

^C 2 ^H 5

HN-CH ₀ CH ₀ CH ₀ -N
I 2 2 2

C ₂ H ₅

C ₂ H ₅

CH. CH.

21.5

ro cn cn co

Example number R _f -Thiol Kati onen-aktiv

link

γ cL'yn / cm

13th

R _f C ₂ H ₄ SH

^C 2 ^H 5

18.8

14th

15th

R _f C ₂ H ₄ SH

^C 8 ^F 17 ^C 2 ^H 4 ^SH

.

^C 2 ^H 5

C ₂ H ₅

NH.

21.2

17.9

16

^C 8 ^F 17 ^C 2 ^H 4 ^SH CH ₂ NH ₂

21.4

ro cn cn co

Example number

R _f -thiol cation-active compound

γ dyn / cm

HN H N-CH ₃

^C 8 ^F 17 ^C 2 ^H 4 ^SH

CH ₃ NHCH ₂ CH ₂ CH ₂ Nh ₂

■ ·.:. H ₂ NCH ₂ CH ₂ CH ₂ NH ₂

17 2 °° • ^ CD

Example 22

2- or. -5- (l>l> 2 _y 2-tetrahydroperfluorodecylthio) amber acid mono- [2- (N, N-dimethyl) aminoethyl] ester

j Q / 2. and isomer

Z 2 2 s.

^CH 3

Ν, Ν-Diinethylaminoäthanol (0.040S mol, 3 * 64 g) in acetone (10 g) at 10 ⁰ C with the solution of maleic anhydride (0.0408 mol, 4.00 g) in acetone (15 g). The product precipitates as an acetone-insoluble resin. After 30 minutes, methanol (20 g) is added, a dispersion being formed. 1,1,2,2-tetrahydroperfluorodecyl mercaptan (0.0408 mol, 19.6 g) is added, a clear solution forming as the reaction proceeds. The batch is left to stand at room temperature for 24 hours. GC and DSC show no unreacted mercaptan. Drying the yellow solution in vacuo gives a light yellow wax. The yield is 26.5 g (98.5%).

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

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

- 71 609828/1043

It. ♦ '

Example number

R _f -thiol cation-active compound

γ "dyn / cm

^C 8 ^F 17 ^C 2 ^H 4 ^SH -N (CII ₂ CH ₂ OH)

KO-CH (CH ₃ ) -CH ₂ N (C ₂ H ₅ )

19.0 17.8

CD
CO
OD

^C 8 ^F 17 ^C 2 ^H 4 ^SH

17.4

26th

^C 8 ^F X ^{7 C} 2 ^H 4 ^SH

17.4

^C 8 ^F 17 ^C 2 ^H 4 ^SH ? 18 ^H 37

-N ·

- (CH ₀ CH ₉ O) H 26.3

χ + y β 15

28

" ^C 6 ^F 13 ^C 2 ^H 4 ^SH HO-CH ₀ CH, -N-CH, CH _ -OH 2 j 2 2

21.2

ro cn cn co

(DO CO

Example 29

2- or 5- (l, l '2, 2, -Tetrahydroperfluordecylthio) succinic acid mono- (2 ^t -chinolinoäthyl) -e he st

C ₀ F CII ~ CH_ S-CHCXX

isomer

The stirred solution of 2- (2-hydroxyethyl) quinoline (0.0255 mol, 4.2 g) in dichloromethane (20 g) is mixed with the solution of maleic anhydride (0.0255 mol, 2.5 g) in dichloromethane (10 g), the mixture is cooled to 0 ⁰ C and holding the mixture during the addition at -10 ⁰ C. upon complete addition, removed heat the dry ice / acetone bath and the reaction mixture is slowly at 20 C. Then 1,1,2,2-tetrahydroperfXuordecylmercaptan (0.0255 mol, 12.24 g) is added. The brown solution is left to stand overnight at room temperature and then warmed to 26 ° C. for 2 hours. DSC and GC show none. unreacted mercaptan. The solution is dried in vacuo and 18.2 g of light brown powder (94.8%) are obtained.

The surface tension (γ) of the aqueous solution of the above-mentioned compound is 22 dyn / cm.

Example 30

N, N ^t -Bisr (n-propyl-5) -2- or ~ 5- (l, l, 2,2-tetrahydroperfluorooctylthio) succinamic acid monoamido-ipiperazine

609828/1043 ⁷³ ~

2559Τ89

6 13 2 2. j _{θ /} ^

_n CKlICH _n CH _n CH ₀ Ii H NHCH-CH-CH-IJCCH., 2η 2 2 2 _{| iV} _ _y 2 2 2 ^ 2

and isomer.

A maleic anhydride solution (0.0510 mol, 5.0 g) cooled with dry ice / isopropanol is added dropwise at -10 to OC with 1.4-bis (3-aminopropyl) piperazine (0.0255 mol, 5 >> 1 g) in 10 g acetone. A white precipitate separates out immediately, and the reaction mixture is ^{stirred at 20 °} C. for one hour.

1,1,2,2-tetrahydroperfluorooctyl mercaptan is added (0.0510 mol, 19.27 g) and stir the batch for 3 days at room temperature until DSC shows no traces of unreacted Mercaptans shows more. Drying the amber-colored solution in a high vacuum gives 29 ^ 1 g of yellow powder (99% yield).

The infrared spectrum agrees with the constitution match.

The surface tension (γ) of the aqueous solution of the above-mentioned compound is 22 dyn / cm.

Example 31

N- [3- (Pimethylamino) propyl] -2.- or -3- (heptafluoroisopro "Doxy ~ 1,1,2,2-tetrahydroperfluoroalkylthio) succinamic acid

^, CFO (CF ₀ ) CH-CH-S-CH-COO® ^

■ ^ 2. η 2 2 ι Qy

2 2 2 2 ¹ ^

and isomer

- 74 -6Q9828 / 1CU3

Maleic anhydrides (0.0255 mol, 2.5 g) are dissolved in 10 g of acetone and 3-dimethylaminopropylamine is added dropwise (0.0255 mol, 2.61 g) in 5 g of acetone in such a way that the reaction temperature is kept at 5-10 ° C. With advancing Reaction forms an acetone-insoluble resin; when the addition of amine is complete, 10 g are added Methanol to form a uniform mixture.

Heptafluoroisopropoxy-l, l, 2,2-tetrahydroperfluoroalkylmercaptan is added (0.0255 mol, 14.60 g) and stir the reaction mixture for 2 days until DSC shows no traces of mercaptan shows more. Drying the pale yellow. Solution in vacuo results 18.9 g of white powder (95.9% yield).

The infrared analysis agrees with the above constitution.

Example 32

N- [3- (Diniethylamino) propyl] - 2- or -3- (1,1 * 2,2-tetrahydroperfluorooctylthio ) methylsuccinamic acid

I ■

CH-COO

isomer

The cooled solution of itaconic anhydride is added (0.025 mol, 2.80 g) in 10 g of acetone at 5-10 ° C with 3-dimethylaminopropylamine (0.25 mol, 2.55 g) in 5 g of acetone. An immediate exothermic reaction takes place, and light-

~ 75 609828/10 43

brown product slowly precipitates. To dissolve the product, 10 g of methanol are added and the reaction mixture is stirred for one hour.

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

The infrared analysis agrees with the above constitution.

Example 33.

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

Dissolve 41.7 g (0.061 mol) of the surfactant prepared according to Example 1 in the same amount of acetone, mixed with 7 "45 g (0,06l mole) propane sultone and the reaction mixture stirred for 8 hours at 50 ⁰ C j, the IR spectrum has a strong new band at 1035 cm -1, indicating sulfonate formation; a C = 0 band at 1660 cm "" and bands at 1780 and 1710 cm indicate a certain imide formation. No carboxylate or dimethylamino groups are visible in the IR spectrum, which is generally in accordance with the constitution shown below. The product is waxy and solid and results in a strongly foaming aqueous solution.

- 76 -

609828/10 43

2559T89

CpF ..CH _{1 0} CH ₀ -SC-COOH

CH-CON-CH ₀ CH ₀ CH ₀ -N-CH ₀ CH ₀ CH _n SO ⁰ * H ²²² | Φ 2223

CH ₃

and its isomer.

Elemental analysis: C μ α τ? Calculated: 33.6 3.4 7.6 39.6

Found: 33.1 3.5 8.0 38.7

The surface tension (Ύ _ο ) of the aqueous solution of the above-mentioned compound is 21.5 dynes / cm.

When it is heated to 120 ^° C. for 30 minutes, its IR spectrum changes. The band at 1660 cm "disappears completely and the two imide bands at 1780 and 1720 cm" become very strong. There is no carboxylate and no dimethylamino absorption. This IR spectrum is consistent with the constitution:

^ n

CH ₃

S. * * A ~ ^CH 2 ^CH 2 ^CH 2 ^SO 3 "

2 - <\ ^j

O ³

The surface tension (γ) of the aqueous solution of the above-mentioned compound is 22.5 dynes / cm.

Example 3A-

Example 33 is repeated with the FL> -substituted Succinamic acid from Example 16. The sulfonate (A) forms

- 77 609828/1043

easily and is a waxy, brown pest. When heated, imidation takes place to connect the Constitution (B) instead of:

C ₈ F ₁₇ CH ₂ CH ₂ -S-CH '

COOII

^ ΛΛΥΊΤΤ / ~ O T / / ~~ "\ \ r '

. CONH-CH- (OiP-- CH-CH ₀ CH ₀ SO ^ (A)

** \ —— / -w rf * J & O

φ heat O

The surface tension (γ) of the aqueous solution

above compound is 19.1 dynes / cm.

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

Elemental analysis of (B) '.

Calculated: 33.4

Found: 34.6

This example illustrates the formation of R “-substituted groups Succinimides from the corresponding succinamic acid.

The IR analysis of the compound prepared in Example 1 shows a strong carboxylate band at 160 cm "" and

N S. F. 3.4 7.7 38.8 3.3 8.1 37.2 Example 3

609828 Π 3% 3 "

a strong C = O band at 1660 cm -1, consistent with the Constitutions:

C ₀ F _n --CH ₀ CH ₀ -SC-COO 8 17 2 2 j

CH ₀ -CO-N-CH ₀ CH ₀ CH ₀ M (CH-) HH

or

C ₀ F _n ^ -CH ₀ CH ₀ -SC-COH-CH ₀ CH CH N (CH ^) 8 17 2 2, 2 2 ^ J

When heated to 120 ^° C. for 20 minutes, this material foams weakly; it becomes insoluble in water but dissolves in acidic aqueous medium. Its IR analysis shows two strong bands characteristic of cyclic imide at 1780 and 1710 cm -1, while the bands at 1600 and 1660 cm -1 are reduced to weak shoulders; strong _} absorption characteristic of the dimethyl amino group at 2770 and 2820 cm ~ is also present. The spectrum is consistent with the constitution:

H °
C ₈ F ₁₇ CH ₂ CH ₂ SCC CH ₃

/ N CIUCIUCiU N ^{'v J}

CH-C ^.

N- (N ', N-dimethyl-3-aminopropyl) -2- (1,1,2,2-tetrahydroheptadecylfluorothiodecyl) succinimide «

- 79 609828/10 43

S. F. 4.7 47.5 5.3 46.4

Elemental analysis for (B):

C .N

Calculated; 33.4 4.1 Found: 34 * 2 4.0

The following examples describe the production of further quaternary derivatives.

Example 3β

2.04 g (0.003 mol) of [2- or .3- (l, l, 2,2-tetrahydroperfluorodecylthio)] -N, N-dimethyl (3-aminopropyl) -sucinamic acid (from Example 1) are dissolved in 5 cm 35% aqueous HCl, the clear solution evaporates and the residue is dried in vacuo (0.1 Torr) at 80 ^° C. for 12 hours, giving 2.1 g of white powder of the following constitution:

C ₀ F., .CH ₀ CH ₀ SCH-COOH

Ch ₂ -CONH-CH ₂ CH ₂ CH ₂ N (CH ₃ ) η Cl

and isomer.

The surface tension (j _q ) of the aqueous solution of the above-mentioned compound is 18.8 dynes / cm.

Example 37

2.04 g (0.003 mol) of 2- or -3- (l, l, 2,2-tetrahydroperfluorodecylthioJ-NjN-dimethylaminopropylsuccinamic acid, which melts at 123-128 ° C.) are melted together with 0.43 g (0.003 mol) of methyl iodide in 10 g of isopropanol in an ampoule, heated for 3 hours, filtered, the pale pink suspension and dried to give 1.6 g melting at 205-250 ⁰ C a white powder following constitution is obtained:

6 0 9 8 2 8/1

The surface tension (γ) of the aqueous solution of the above-mentioned compound is 24.9 dynes / cm.

Example 38

2.04 g (0.003 mol) of 2- or -3- (l, l, 2.2 ~) are heated Tetrahydroperfluorodecylthio) -N, N-dimethyl (3-aminopropyl) succinamic acid with 0.38 g (0.003 mol) of benzyl chloride in 10 g of ethanol under reflux, not until basic tertiary amine is more detectable. The solution is evaporated and gives 2.17 g of a whitish semi-solid mass of the constitution

'CH-C- ⁰
j NCH ₂ CH ₂ CH ₂ N (CH J ₂ CH ₂ - \ Λ Cl *

CH-C ^
O

• The surface tension (γ _ο ) of the aqueous solution of the above-mentioned compound is 20.8 dynes / cm.

Example 39

2.04 g (0.003 mol) of [2- or -3- (l, l, 2,2-tetrahydroperfluorodecylthio)] - N, N-dimethyl (3-aminopropyl) succinamic acid are stirred overnight with 0.28 g (0.003 mol) of chloroacetic acid in 30 g of water. Free tertiary amine cannot be detected. For defoaming, 20 g of methanol are added and

- 81 609828/1043

the clear solution is evaporated at 6O ⁰ C in a vacuum to obtain 2.1 g of whitish wax the following constitution:

C ₀ F _1n -CH ₀ CH ₀ SCH-C

OX / <L /. ,

NCH ₀ CH ₀ CH ₀ N (CH,) CH ₉ COO

/ Z. A c. J Λ £ ·

The surface tension (γ) of the aqueous solution of the abovementioned compound is 17 »4 dynes / cm.

Example 40

2.04 g (0.003 mol) of [2- or -3-1,1,2,2-tetrahydroperf luordecylthio] -N, N-dimethyl (3-aminopropyl) succinamic acid are dissolved in 30 ml of ether and added dropwise within 5 minutes at 15 ⁰ C with the solution of 0.22 g (0.0031 mol) of ß-propiolactone in 5 ml ether. The mixture is stirred for 2 hours at 30 ° C. and the ether is removed on a rotary evaporator. Yield: 2.2 g of a product of the constitution:

C ₀ F _n -CH-CiLS-CH-COOH • ο X / 2 2 j

N (CH ₃ ) ₂ CH ₂ -CH ₂ COc

and isomer.

The surface tension (ύ _ο ) of the aqueous solution of the abovementioned compound is 22.6 dynes / cm.

- 82 -

609828/1043

Φ Φ TJ CM CM I. CM N " ^ » CM I. ιη 1 φ CM ι κ >> φ 2559 18th 9 • Ti B. • Η TJ W. I CM Fh ι
Γ \ | do Fh H Fh • Η ο CQ
r-t Ν> N ^ -H O Cv 3 ι ⁰ U O H 3 CQ Φ CQ fa K S. ο Kd HCM CD ad • Η CQ EH O O CD O O AH CQ O & Η Fh CQ CJ φ CQ φ I. cj -p'l TJ Xi .- O TJ -μ TJ Ö CD EH CH • Η M. + § ΦΗ ■ Η + § • PH 3 • Η H • Η • Η Oi ο CM CM S ^ S. ω ν_ ^ H sd CQ φ O • H f CD S I Ch CD Xi Ci -P ^ CM "~ CvJ 3 CM '"cm TJ t ^ i Ö
• Η CM Fh α
• Η U α) CD 0.1 Fh CQ W. K I I Ü tr! Φ O φ EH bO H Φ ο O / ~ ~ ^ O ü O O Pl O > O • Η
CD • Η V • O S 3 O 3 • H EH Fh
O • Η Κ— *> £ CQ 's— U CQ B.
• Η Xi
O OUI 3 O O - N O Ti CQ O H O O -P O ü Si! O ! >> U -H ¹ H. O ü H CM CM I. CM CD Xi TJ CM >> K - I. K Fh id ω ö Φ K ^ CM O O CMCM O -μ CH it φ Fh ' O ¹ O
γ ^ H ΐ'ΐΜ i ~ CM ν, J I ^ CM φ CD ö Φ f * M CJ
CM CD O O I _. .. O -μ bO 03 H H -P Ό Fh O O SH O £ Η Φ Φ O O O O O ν ' I!>, ν ' j3 TJ N 3
H CD te HXi Ci Ö >> Pl κ " ^ K CH Fh O ü ί »-Ρ Ü H C) • Η υ O Fh 3 co CO ■ ρ ο CO CM
fa
O Xi Φ Ci CD ω CO Φ « CM CM ω ö CM H φ
-μ Ö ω CM CM PiCQ do 1 do <! · Η K I. O CQ Φ H (D K O ü ι O »—Χ φ > -P ο O CM O CM S cd CM O TJ Xt • Η X φ φ CM CM K -H O do • Η -μ ω Ti K • Κ O Xi O • Η ü j3 H j « K CD O ί £ O CH -P CH «Η ■ μ CD φ S. Ch t <l <H cü H oi -μ oi -Hh ^ H Γ I. Ci oi rQoi >> H TJ I Η • • ^. ω ^ J Ν "\ J fa Fh H φ H Λ5 S. O • Η |> I. • ° i CD <! H S £ O ω ο H CM Fh CD ·. N K \ H H EH t- Fh £>, S. O Fh - Xi H (D H I TJ AH 3 O S. fa • Η Fh CM H ι—,>, HP ~ H ω 3 I I VD Pl ω H Hi? ωπ CH Fh H - CM O CQ TJ CQ CQ ί >> cd Fh 3 Ch CM! • Η 3 Φ • Η Pi Fh •HI Φ ad Fh CQ Φ ö Ci H rQ Ο-Ρ TJK ^ Pl CQ φ Υ "η 3 Ph φ H Fh Φ I I O TJ Ρ · S >> CD bO Xi Φ H Pip , Fh • Η O I pi Cj ο , Q f S TJ Fh HO Xi • Η CQ CD CQ O CM CD TJ >, Fh O CQ • Η EH β φ Ci ~ ■ s • Η ί >> Ä pl
-μ ο ■ Η Φ 30th S. Φ Fh • Η CM S.Q Fh O 'S H • Η CD H- ote I. -P O Fh S-H Xi <: bO Φ cd H - I. Φ 3 -μ I B O ω H • Η Qi H «■ CMCM -P CQ φ S cd scd hO Φ Pl
CQ ί> ^ Η -μ CQ Φ • Η -μ • Η <ij Y ^ -> Fh -JR -ρ Φ ί * Υ SH Pl Φ I. ■ Η FQ Φ ΚΛ I> ■ 3 S. • B. α
H B I ΗΛ CD O CQ • Η >> - P <t- Xi CQ Φ hO 3 * Ä = cd
-PO H ω α <! Fh = j3 ιό, α S-H • Η Φ O CQ ι ι T B φ • d 1Λ 33 I I S cd SCM -μ
CQ ο ·· ■ Η CQ ω φ H < Ö CH • Η Oi CM CQ Φ CM • Η H H Xi <! <;

- 83 609828/1043

Q)

O
fa

Q) HH

CM

CvJ

(M

CJ

O O (M

Πα]

"ffi

O CO

K
O (M

O O

co

CM

O CM

O ΓΗ

ω ο

(M W O

O O

<Μ K O

O O

O CO

CM K O

O H

CM

Ua OH

LPv

00

0 9828 /

Table 2

Anion-active fluorinated surfactants used in Examples 41-117

I.
co
VJl
I. Anion-active s
R _f surfactant Surname Formula - "100%, or how
specified, active Bl Perfluoroalkane acid R _f CO _? H 8609 B2 Potassium perfluoroalkanoate 25% R ^ COpK - 25% in 10% hexylene glycol /
15% t-butyl alcohol / water ro
CO B3 2,2-dihydroperfluoroalkanoic acid R _f CH ₂ CO ₂ H O
-P-
u> B4 Sodium !, 1,2,2-tetrahydropic
fluoroalkylthiopropanesulfonate
^R f ^{= C} 6 ^C 8 ^C 10 R _f CH ₂ CH ₂ S (CH ₂ ) ₃ SO ₃ Na B5 Perfluoro
heptanoic acid 75 25 O C ₆ F ₁₃ CO ₂ H Ββ Perfluorononane
acid 4 87 9 C ₈ F ₁₇ CO ₂ H B7 Perfluorun
decanoic acid O 11.5 88.5 C ₁₀ F ₂₁ CO ₂ H B8 Potassium perfluoroheptanoate C ₆ F ₁₃ CO ₂ K - 25% as in B2

with R typically as a mixture of C ₆ F ₁₃ (32%), (6%) and traces of other homologues

(62%) and

Table 3
Ionic (and amphoteric) surfactants used in Examples 41-117

Ionic type A anion-active
Surfactant K cation-active

AM - Amphoteric Name - Active% as stated or "100%

Trimethylamine laurimide

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

N-Lauryl-myristyl-ß-aminopropionic acid (50%) coconutimidazolinium ethosulfate
Dimethyl (2-hydroxypropyl) amine laurimide, dimethyl (2-hydroxypropyl) amine myristimide, dimethyl (2-hydroxypropyl) amine palmitimide, trimethylamine myristimide
Acylamidoammonium sulfonic acid betaine (50%) Amphoteric dicarboxylated Laurinimidazolinium-ro derivative (38%) cn

Sodium salt of ethoxylated lauryl alcohol <£> sulfate (27%) - ^

Disodium salt of N-lauryl-.beta.-iminodipropion- ^co acid

I.
00 Cl AT THE S. I. C2 AT THE 9828/1 04 C3
C4
C5 . AT THE
K
AT THE C6 AT THE C7 AT THE C8 AT THE C9 AT THE ClO AT THE CIl A. C12 AT THE

Table 4
Nonionic surfactants used in Examples 41-117

Nonionic name

Surfactant active% as indicated or-ΊΟΟ ^

Dl octylphenoxypolyethoxyethanol (12) 99? O

D2 polyoxyethylene (23) lauryl ether

D3 octylphenoxypolyethoxyethanol (16) 70%

D4 octylphenoxypolyethoxyethanol (10) 9956

D5 octylphenoxypolyethoxyethanol (30) 70%

D6 nonylphenoxypolyethoxyethanol (20)

D7 nonylphenoxypolyethoxyethanol (30)

DS Branched Alcohol Ethoxylate (15)

The numbers in brackets mean recurring ethylene oxide units.

Table 5
Solvents used in Examples 41-117

Solvent name

El. 1-butoxyethoxy-2-propanol

E2 1-butoxy-2-propanol / 2- methyl-2,4-

pentanediol in a ratio of 2: 3

E3 diethylene glycol monobutyl ether

E4 2-methyl-2,4-pentanedi oil

E5 Tetrahydrothiophen-1,1-dioxide

E6 ethylene glycol

- 87 609828/1043

TO

Examples 41 to 44

The AFFF agents composed as shown in Table 6 have identical compositions except that the R ~ group in the amplified PU surfactant differs from a pure perfluorohexyl over a pure perfluorooctyl group to a pure perfluorodecyl group as well as a mixture of perfluorohexyl, Perfluorooctyl and PerfTuordecyl in approximate proportions 1: 2: 1 is modified.

As the surface tension data in Table 6 show, the lowest values are obtained with the pure Cg isomers followed by the amphoteric R ~ surfactant with mixed R ^ groups. On the other hand, you get the lowest Interfacial tension values with the Cg isomer and the R n isomer mixture. As a result, you get the highest Spreading coefficient of 6.5 dynes / cm with the R ^ mixture, R ^ -mixed amphoteric fluorinated surfactants of type A with mixed R "groups are, of course, from the standpoint of Economic efficiency is highly desirable.

Unless otherwise indicated, the pH values of the compositions are in these two examples below generally in the range of 7 to 8.5.

- 88 -

609828/1043

CTj O CO OO

Tabel

Effect of the amphoteric FU surfactant (component A) and its homolog content

Example Nm. 41 to

Various amphoteric Rf surfactant solutions: (as indicated)

Anion-active Rp surfactant Bl: 0.29%

Amphoteric auxiliary surfactant C2: 8.33% (50% solids)

Additional auxiliary surfactant C4: 0.83%

Nonionic auxiliary surfactant P2: 2.08%

Solvent. . El: 5.00%

Water rest

Example no.41 42 43

R - surfactant A6, 30% as present 4.93 R _f - surfactant AY, 30% as present 4.93

R _f surfactant A8, 100% as present 1.48

R ^ surfactant Al, 30% as in the present case 4.93

Surface tension ² * dyn / cm 17.7 16.9 18.0 17.2 Interfacial tension ³⁵ dyn / cm 0.9 1.7 1 * 7 0.9 Spreading coefficient ³ * dyn / cm 6.0 6.0 4.9 6.5

3 €

Diluted to 3 percent with distilled water; Interfacial tension against Cyclohexane

K5 cn cn CD

oo CD

Examples 45 to 50

The AFFF agent compositions listed in Table 7 have an identical composition, with the exception of the anion-active fluorinated surfactants of type B, which are from a perfluorohexyl via a perfluorooctyl to a perfluorodecyl group and mixtures as defined in Table 2 R ^ groups are modified. The lowest surface tension data obtained with perfluorooctyl and a mixed perfluoroalkyl group containing nonionic surfactants des Type B. These preferred compositions also show the greatest rate of film spreading.

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

Examples 51 to 57

The measurements of the surface properties shown in Table 8 show that aqueous solutions of amphoteric R ~ surfactants of type A have low surface tensions, but have high interfacial tensions (measured against hydrocarbons such as cyclohexane), and such aqueous solutions therefore have negative spreading coefficients. The addition of amphoteric auxiliary surfactants of type C to aqueous solutions of amphoteric R ~ surfactants of type A

- 90 6 0 9 8 2 8/1043

makes it possible to lower the interface properties and to achieve these very high spreading coefficients. Amphoteric auxiliary surfactants of type C are therefore used as border " surface tension reducers, although they adhere to other properties of the AFFF agents such as foaming, stability, etc. contribute. Examples 51 through 56 show how the Interfacial tension of a 0.1 percent aqueous solution of the amphoteric FU part A5 by adding the in table 3 listed, preferred fatty acid aminimide surfactants of Type C is reduced from 7> 1 dyn / cm to below 1.0 dyn / cm; the spreading coefficient increases from -1.1 dyn / cm to 5> 6 dyn / cm. A typical non-ionic surfactant D4 is much less effective.

- 91 -

609828/1043

cn o co

Tabel

Effect of the anion-active R _f ~ surfactant and its homolog content

Example nos. 45 to

Amphoteric R _f surfactant solution '. . .Al: 4.93% '(30% solids)

Anion-active R ^ surfactant Various:

Amphoteric auxiliary surfactant. . . .C2:

Another amphoteric auxiliary surfactant C3:

Nonionic auxiliary surfactant D3:

Solvent El: 5.00%

0.29%

8.33% (30% solids)

1.66% (70% solids)

2.97% (70% solids)

Water Rs si

Example no.

Anion-active R., Surfactant as indicated

R «homolog

Surface tension dyn / cm Interfacial tension dyn / cm Spreading coefficient "dyn / cm

Film spread rate, sec, reseal property

45
without

46 47 48 49

B5

Cr B6
^C 8

B7 C

10

Bl mixture

50

B3 mixture

19.5 18.1 17.5 17.7 17.7

1.0 0.6 1.2 1.7 1.0

4.1 5.9 5.9 5.2 5.8

17.5 1.0 6.1

very 13 5 38 9 slow

no good good sclifedit good

5 good

³⁵ Diluted to 3 percent with distilled water; Interfacial tension against
Cyclohexane

Tabel

Surface properties of amphoteric Rp surfactant vamphoters

Auxiliary surfactant solutions

Amphoteric R ~ surfactant solution A5: 0.1%

Auxiliary surfactants - various $ 0.1

Water ..... rest

Auxiliary surfactant surfaces Interfaces Spreading without tension tension coefficient example C5 dyn / cm dyn / cm - 1.1 51 C6 18.6 7.1 5.6 52 C7 18.4 0.6 5 * 2 53 Cl 18.8 0.6 4.2 54 C8 20.2 0.2 5.1 55 D4 18.6 0.9 4.8 56 19.3 0.5 1.2 57 19.6 3.8

Examples 58 to 63

The AFFP agents with a composition as listed in Table 9 are identical with the exception of various non-ionogenic aliphatic auxiliary sterisides of type D. Comparison of the surface tension and interfacial tension data shows that almost identical values are obtained up to 0.5 of a dyn / cm and all samples have excellent compatibility with seawater, while the only sample that does not contain any nonionic carbon surfactant of type D results in heavy precipitation when diluted with seawater and aged for 10 days at 65 ° C.

- 94 809828/10 43

Tabel

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

Amphoteric R _f surfactant solution Al: 4.93% (30% solids)

Anion-active R _f surfactant Bl: 0.29%

Amphoteric auxiliary sulfide C2: 8.33% (30% solids)

Additional amphoteric auxiliary surfactant C3: 1.66% (50% solids)

Nonionic auxiliary surfactant. . .Miscellaneous: 2.08% (as 100% solids)

Solvent El: 5.00%

Water rest

Example no.

58

60 61 62

Nonionic auxiliary surfactant as indicated without D3

D6 D7

Surface tension dyn / cm Interfacial tension 'dyn / cm Spreading coefficient dyn / cm compatibility with sea water when diluted to 6%, 10 days at 65 C

63

D8

18.0 17th , 3 17.4 17.0 16, 9 17, 5 1.7 1 , 2 1.4 1.3 1, 3 1, 6th 4.9 6th ,1 5.8 6.3 6, 4th 6, 0 stronger
Low
blow clear clear clear clear clear

Diluted to 3% with distilled water; against cyclohexane

Interfacial tension

Examples 64 to? 8

AFFF means for 6 percent dosage sit with a content of. 2 carbon percent by weight of different solvents, but otherwise identical compositions as given in Table 10, are assessed using the open-air foam test method to determine the spread of sclia of a 6 percent dilution of the new AFFF agents in synthetic seawater. As the data in Table 10 shows, simply by varying the type of solvent used in the AFFF agent, spreading ratios in the range of 4.0 (high density foam) to 11 jO (lower density foam) can be obtained. It is important from both an ecological and an economic point of view that one can achieve such a wide foam spread range with such a low (2 percent) solvent content «

- 96 -

609828/1043

O (O CD

Table 10

Composition of AFFF agents Example Nos. 64 to 78

Amphoteric R - surfactant solution ........ Al: '

Anion-active R ~ surfactant ........ Bl:

Amphoteric auxiliary surfactant Cl:

Nonionic auxiliary surfactant. . Dl:

Solvents, various

water

3.07%
0.19%
3.00%
3.00%
2.00%
rest

example

No.

solvent

Foam spread

Example no, solvent

Foam spread

64 Without 4.2 72 65 Diethylene glycol monobutyl
ether 7.9 73 66 Diethyl glycol diethyl ether 4.2 74 67 N-methyl-2-pyrrolidone 4.1 75 68 Tetrahydrothiophene-1,1-dioxide 4.3 76 69 t-butane cl 6.3 77 70 N, N-dimethylformamide 5.3 78

Butoxy-2-propanol 11.0

Dipropylene glycol mono- 5 1 0 ethyl ether

Proylene glycol mono- 4.1 ethyl ether

2-methyl-2,4-pentane-6.2 diol

Propoxy-2-propanol 7.2

Dipropylene glycol 4.0

1-butoxyethoxy-2-11, O propanol

71 ■ Ν, Ν-diinethylacetamide

4.5

Examples 79 to 82

APPF agents with compositions indicated in the table are assessed and compared with a commercially available AFFF agent, Light Water FC-200, in 2.60 m ² fire tests, ie the control time, extinguishing time and re-ignition time data are achieved higher performance with the new AFFF agents with a fluorine content in the product reduced by up to half; compared with FC-200, approximately the same control time, extinguishing time and re-ignition time are achieved with the AFFF agent from example 82, which is only 0.8 Percent fluorine, compared to 2.1 percent fluorine in FC-200. These results indicate the higher effectiveness of the new AFFF agents and the less importance of foam spreading as a performance criterion for better film properties.

- 98 -

609828/1043

Table 11

Comparative fire test data ⁵ * for AFFF agents

Example Nm. 79 to 82

CD CD CO 00

Amphoteric R ~~ surfactant solution Nonionic auxiliary surfactant

Al: Various ( 30% solids) Dl: Various (100% solids)

Anion-active R ~ surfactant Amphoteric auxiliary surfactant. Solvents ..... Water ο

Bl: 0.35 per cent

Cl: 2.25%

E2: 6.25%

. . rest

(based on solids) (100% solids)

Example no. 79 80 81 82 FC-200 R “surfactant Al,% as in the present case
Nonionic surfactant Dl,% as above
lying 8.40
1.80 7.00
1.50 5.60
1.20 4.66
1.00 % F in the formula 1.44 1.20 0.96 0.80 2.10 Control time, sec.
Deletion time, sec.
Reignition time, min. 29
44
8:15 30th
34
10:30 34
47
5:45 34
51
4:58 33
52
5:30 Foam spread
Drainage time to 25%, min. 5.5
4:42 5.6
4:00 5.4
4:15 4.7
3:45 7.0
5:03

Diluted to 6% with sea water, tested on a 2.60 m fire

cn cn co

Examples 83 to 85

AFFF agents with the composition shown in Table 12 as well as with various R ^ surfactants of type B and various solvents of type E, or with none at all

Solvents, are assessed by 2.60m fire tests using a 6.57 liter per minute nozzle. As the test data in Table 12 shows, high-density foams with a foam spread of less than 5 and even 3-7 are obtained with no solvent-containing AFFF compositions, while a solvent content of 35 percent increases the foam spread with this AFFF composition up to 8.5 _o A comparison with the commercially available FC-200 shows that gives slightly better extinguishing times in example 83rd

- 100 609828/1043

Tabel

³⁵

Comparative ^{fire test data 35} for AFFF agent Example Nos. 83 bis

O CD CO N. "> CO

Amphoteric R _f surfactant solution Al: 7.1 (30% solids)

Anion-active R _f Surfactant Various (100% solids)

Amphoteric Hiifstinside Cl: 3.0

Nonionic auxiliary surfactant .... Dl: 3.0

Solvent Various

Water . . ο. rest

Example no. 83 84 85 FC-200 Anion-active R _f ~ surfactant Bl,
% as in the present case
Anion-active R ~ surfactant B4,
% as in the present case
Solvent E3 0.33
35 0.33
without 0.50
without Sweet sea
water Sweet sea
v / ater Sweet sea
water SüP sea
water Deletion time, sec.
Reignition time, min.
Foam spread 40 46
6:00 am 6:00 am
8.5 7.7 55 SUN
8:44 3:20
3.8 3.8 67 83
8:05 3:27
4.8 3.7 52 52
6:30 am 5:30 pm
7.0 7.0

Diluted to 6 percent with fresh or sea water, tested on a 2.60 m fire

ro cn cn

Examples 86 to 90

The AFFF agents with the composition given in Table 13 are assessed by 2.60 m fire tests. The performance of these AFFF agents containing various Type C auxiliary surfactants results in excellent control times (down to 26 seconds) and very short erase times (down to 37 seconds), and two of the compositions (Examples 88 and 90) already put out the fire

shortly after the pan used in the 2.60 m fire test was removed, demonstrating the superior sealing properties of the shows new AFFF agents compared to commercially available products.

- 102 609828/1043

Table 13

Comparative ^{fire test data 3} * for AFFF agents
Example nos. 86 to 90

Amphoteric R ^ surfactant solution
Ionic (and amphoteric) auxiliary surfactants.
Nonionic auxiliary surfactant
Solvent <· 86 Al:
Bl:
Dl:
E: 5 ρ9% (30% solids)
0.35% (100% solids)
Different
1.2
6.0
rest 89 90 Cl
C2 Example. No. C3
C2 87 88 Cl
ClO 26th
38
4:35 from ⁺ Auxiliary surfactant - 1% solids
Auxiliary surfactant - 2% solids 26th
39
7:31 Ch
C2 Cl '
C9 33
45
7:56 6.6
5'-55 Control time, sec.
Deletion time, sec.
Reignition time, min. 5.9
5:19 27
37 33
48
5:02 out of ⁴ " VJl VJl
O VO
VJl Foam spread
Drainage time to 25%, min. 6.2 6.7
5:20

κ Diluted to 6% with sea water, tested on 2.60 m fires
+ Fire completely extinguished

cn cn co

Example 91

An AFFF agent of the composition shown in Table 14 is at one on a level, with 1,135 πι (300 gallons) of gasoline filled 12.19 m round area

Fire placed 117.05 m in diameter using a double-shielded Rockwool FFF nozzle with one discharge rated at 1 189.27 per minute. An excellent foam spread of 9j0 is obtained; the fire is quenched quickly and is almost completely erased within the diked area. The reignition is minimal, and the "Summation of percent erasure" exceeds 320 by far the military specification F-24385 (Navy).

- 104 -

B0982 8 / 1Ü43

Table 14

Fire test of the preferred AFFF means in the 117.0 m fire test

Example No. 91

Amphoteric R _f surfactant solution Al: 5.93% (30% solids)

Anion-active R surfactant Bl: 0.35%

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

Another amphoteric auxiliary surfactant. . .Cl: 0.50%

Nonionic auxiliary surfactant Dl: 1.20%

Solvents. El: 6.00%

Water .. <> ... rest

Surface tension ³ * dyn / cm. 17.0

Interfacial tension ³⁵ dynes / cm. ...... 1.4

Spreading coefficient ³ * dyn / cm 6.2

Performance in the fire test at Me Erwas server thinning to 6 Frozerfc Excellent attenuation and reflow "Summation of percent extinction" - 320

Foam spread (189.27 1 per minute) ...... 9.0

Drainage to 25% 4:00

Dehydration to 50% 8:41

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

- 105! 509828/1043

Examples 92 Ms 96

AFFF agents of the compositions shown in Table 15 are tested as aerosol-released AFFF agents on 2B fires (name of the Underwriters Laboratory). The results show that the compositions are more effective in extinguishing fires in less time than either or other of the commercially available agents; d. H. Light Water FC-200 or FC-206. According to example 54 is a frost-protected Composition also effective as an extinguishing agent.

- 106 609828/1 043

HO -J

Tabel

Composition and assessment of aerosol-released AFFF agents

Example nos. 92 to

Example no. 92 93 94 95 96 FC-200 FG-SO 6 Amphoteric fU surfactant solution
4.9% as in the present case (30% fixed rate)
Anion-active R _f surfactant, % like
present
Amphoteric auxiliary surfactant,% like
present
Another ionic surfactant, % like
present
Non-ionic auxiliary surfactant, %
as present A2
Bl, 0.24
Cl, 3.0
Dl, 1.0 A2
B4, 0.34
Cl, 3.0
Dl, 1.0 Al
B2, 1.1
C2, 5.0
C4, 0.5
Dl, IiB Al
B2, 1.1
C2, 5.0
C4, 0.5
Dl, 1.75 A4
EU 0.24
C2, 2.0
C4.0.5
Dl, 1.0 Solvent E4, 3% +% white
teres as indicated ¹
Buffer salts, 0.2%, type like
specified> 3
Surface tension dyn / cm
Interfacial tension dyn / cm
Spreading coefficient dyn / cm Fl
18.7
0.9
5.0 F3
ϊ __
i
1 E5, 20.0
Fl
19.3
1.5
3.7 F2
18.1
1.9
3.6 F4
19.6
1.7
3.3 15.9
4.0
4.7 16.3
4.5
3.8

Fire performance properties ^ from aerosol cans on 2-B fires when diluted

Duration of delivery, sec. Foam volume, liter control time, sec. Deletion time, sec.

43

6.7 20 54

32 52 64 49 58 51 6.5 6.0 7.0 6.5 8th 8th 24 23 26th 21 19th 23 46 45 34 37 74 59

Notes on table

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

The aerosol container is a standard can that holds a 430 gram load of AFFF agent as well as a 48 gram load Contains dichlorodifluoromethane.

^ The buffer salts are Fl, Sörensen phosphate with pH 7> 5

F2, Sörensen phosphate with pH 5 »5 F3, Mcllvaine citrate / phosphate at pH 5.5 and
F4, Walpole Acetate at pH 5.5.

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

- ^ Dispensing time, sec. - Time to complete emptying

of the aerosol at 21.1 ° C

Foam volume, liters - total foam volume immediately after

Submission

Control time, sec. - time at which the fire is under control, but still burns. Extinguishing time, sec. - time until complete extinguishing 2B fire - fire on an area of 0.465 m ²

- 108 -

609828/1043

EXAMPLES 97 and 98

AFFF means the composition shown in Table 16 are used with commercially available AFFF agents both of the 6 percent as well as the 3 percent1> dosing type - Light Water FC-206 and FC-203 from 3M and Aer-O-Water 6 and 3 by National Foam - compared. Examples 97 and 98 demonstrate both far superior film spread rates (time up to 50 percent seal) as well more complete and longer lasting seals than available AFFF funds. These factors are effective AFFF composition of fundamental importance.

- 109 -

609828/1043

MO

Table 16

Sealing Properties of AFFF Compositions Example Nos. 97 and

Amphoteric R ^ surfactant solution Al: 5.0% (30% solids)

Anion-active FU surfactant Bl: 0.3%

Amphoteric auxiliary surfactant C2: 8.3% (30% solids)

Another ionic auxiliary surfactant. .. Different

Nonionic auxiliary surfactant ....... Various

Solvent ....... El: 5> 00%

Example No. 97

Aer-0- ¥ ater Aer-O-Water FC FC 98 '6 3 206 203

Auxiliary surfactant Cl 0.4

Auxiliary surfactant C4 - 0.4

Auxiliary surfactant D3 3.0

Auxiliary surfactant Dl - 2.1

Time up to 50% 5
seal 8th 18th Conveyor speed 18th 25th 12th % Sealing 98
in 30 seconds 97 45 Wavenumber 30th 85 72 % Sealing "98
in 120 seconds 98 87 Cuvette length 91 96 87 surface - 20 cm ² - 0.17 ml / min. - 2 930 cm " ¹ - 3 cm Helium flow velocity
speed - 1,000 ml / min.

- 110 -

609828/1 043

EXAMPLES 99-103

AFFF means the compositions shown in Table 17 v / earth fish toxicity studies on Pimephales promelas and Lepomis macrochiriis. Like the results. demonstrate, the investigated AFFF agents have significantly lower toxicity than the control (Light Viater FC-200) and show in addition, a significantly lower chemical oxygen demand than the control, mainly because of the lower Solvent content in the new AFFF funds.

- 111 609828/1043

Tabel

Composition and assessment of APFF funds Example nos. 99'bis

CD O CO OO lsi

Example no. 99 100 101 102 103 FC-200 Amphoteric R _f surfactants
Type +% as -present Al
5.60 A2
5.60 A3
5.60 Al
4.93 A4
4.93 - Anion-active R - surfactants
Bl, % as in the present case 0.24 0.24 0.24 0.24 0.24 - Auxiliary surfactant Cl, % like
present
Auxiliary surfactant C2, % like
present
Auxiliary surfactant C3, % like
present
Auxiliary surfactant Dl, % like
present 3.00
1.50 3.00
1.50 3.00
1.50 8.33
1.66
2.08 8.33
1.66
2.08 - Solvent, type + % E2
6.0 E2
6.0 E2
6.0 El
5.0 El
5.0 Butyl carbitol
34.0 Fish species
Fish toxicity ppm TL-,
(Pimethales promelas) TLe ₀
(Lepomis macro chirus) TL £ g 484
303
190 700
298
129 859
327
124 m *
611
285
133 483
182
69 49 312
16 79
5 20 COD, g Op / liter 0.29 0.31 0.29 0.18 0.70

cn cn co

2559Ί89

EXAMPLES 104-108

AFFF agents for 6 percent dosing with contents of different types of amphoteric auxiliary surfactants of type C and type D, but otherwise identical compositions, are assessed. The comparative evaluation data in Table 18 show (a) that 3 percent solutions of the listed AFFF agents have spreading coefficients between 4.5 and 5.8 dynes / cm and (b) the concentrates themselves have a fish toxicity (Pimephales promelas) between 114 and 524 ppm for TLj-q, \ ias shows that the AFFF agents listed are considerably less toxic than Light Water FC-200 with a TL ₁ -Q of 79 ppm. Table 18 also shows that the AFFF agents listed have a significantly lower chemical and biological oxygen demand (COD and BODj-) than FC-200.

- 113 (3 09828/1043

Table 18

Composition of AFFF funds
Example. Nos. 104 to 108

Amphoteric R ^ surfactant solution Al: 4.93% (30% solids)

Anion-active R ^ surfactant ... Bl: 0.29% (100% solids)

Amphoteric auxiliary inside C2: 8.33% (30% solids)

Other auxiliary surfactants Various

Solvent El: 5.00%

Water rest

Example no. 104 105 106 107 108 FC-200 Auxiliary surfactant Cl,% as in the present case
Auxiliary surfactant C3,% as in the present case
Auxiliary surfactant C4,% as in the present case
Auxiliary surfactant Dl,% as in the present case
Auxiliary surfactant D3>% as in the present case ~ 1.66
2.97 0.42
2.97 0.84
2.08 0.42
2.08 0.84
2.08 - Surface tension dyn / cm
Interfacial tension dyn / cm
Spreading coefficient dyn / cm 18.0
1.5
5.1 17.2
1.6
5.8 18.2
1.9
4.5 18.4
1.4
5.2 18.4
1.3
4.9 15.9
4.0
4.7 Fish toxicity, ppm TL-,
(Pimephales promelas) TL, - _n
^IL 99 434
294
198 880
524
313 480
318
211 447
228
116 160
114
82 312
79
20th COD, g 0 ₂ / g
BOD, mg 0 ₂ / liter 0.19
876 0.20
1 023 0.28
12 300 0.26
10,000 0.25
5 830 0.7
15 600

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

Further optimized AFFF agents for 6 percent dosage, which contain different types and amounts of amphoteric and nonionic auxiliary surfactants of types C and D, but identical amphoteric and anion-active R ~ surfactants of types A and B, are assessed. The comparative evaluation data in Table 19 shows that spreading coefficients in the range from 3.6 to 5.1 dynes / cm are obtained, while the fish toxicity data of the AFFF agent concentrates extend over a range from 294 to over 1000 ppm as TL ₁ -Q for Piinephales promelas A TL greater than 1,000 ppm is considered non-toxic, and products such as the AFFF agents of Examples 112 and 113 are therefore highly desirable from an environmental point of view. Table 19 also reports chemical and biological oxygen demand (COD, BOD ₅ ) of Examples 70 to 73. The very low COD values of 0.19 to 0.22 g of oxygen per liter result mainly from the low solvent content of the new AF FF funds.

- 115 -

609828/1043

CD O CO OO

Table 19

Composition and assessment of AFFF funds Example Nm. 109 to

Amphoteric R ~ surfactant solution Al:

Anion-active R _f surfactant. Bl:

Amphoteric auxiliary substance and non-

ionic auxiliary surfactants:

Solvent El:

water

4.93% (30% solids) 0.29 ° / (100% solids)

Different

5.00%

rest

Example no. 109 • 110 111 112 113 FC-200 Auxiliary surfactant C2,% as in the present case
Auxiliary surfactant C3,% as in the present case
Auxiliary surfactant Dl,% as in the present case
Auxiliary surfactant D2,% as in the present case
Auxiliary surfactant D3,% as in the present case 8.33
1.66
2.08 8.33
1.66
2.97 8.33
1.66
2.08 5.66
0.75 5.66
0.75 - Surface tension dyn / cm
Interfacial tension dyn / cm
Spreading coefficient dyn / cm '18.1
1.3
5.2 18.0
1.5
5.1 18.2
1.5.
4.9 18.1
2.5
4.0 18.2
2.8
3.6 15.9
4.0
4.7 Fish toxicity, ppm, TL-,
(K-mephales promelas) TLr _n
^TL 99 611
285
133 434
294
198 480
318
211 > 1,000
/ 1,000
> 1,000 M 000
> 1,000
> 1,000 312
79
20th COD, g 0 / g
BOD, mg O / liter - ■ 0.19
876 0.22
906 0.20
5 600 0.19
6 830 0.70
15 600

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

cn cn co

EXAMPLE 114

One chooses an AFFF agent of the composition given for example 112 and solutions thereof in synthetic Sea water to show the weak or non-corrosive behavior of the new AFFF agents. According to U.S. more military Regulation MIL-F-24385 Amendment 8, June 20, 1974, shows corrosion tests performed as shown in Table 20 reported that the corrosion observed on various metals and alloys is 10 to 100 times smaller than that permitted in MIL-F-24385, Supplement 8 Maximum values.

- 117 f3 0 9 8 2 Ö / 1 0 4 3

Tabel characteristic

average

Corrosion (milligrams / dm. Day)

A. Metal strips partially immersed in liquid at 38 C for 38 days

Thinning alloy

Concentrate 'Concentrate 6% in sea water
concentrate

Cold rolled steel SAE 1010 Stainless steel (CRES 304) Cupronickel (90% Cu, 10% Ni)

Aluminum βΟβΙΤβ

B. Metal strips completely immersed in the liquid for 60 days at ordinary temperature (0.0254 mm / year)

dilution

alloy

90% in sea water cold rolled steel SAE 1010

90% in sea water cupronickel (90% Cu, 10% Ni)

90% in sea water Monel

90% in sea water bronze 905 (milligrams)

C. Local corrosion - 60 days

Rubber-covered metal strips immersed in liquid at normal temperature for 60 days

dilution

alloy

No

CRES AFFF agent example # 112 2) f

0.16

0.2

0.42

0.24

0.2

0.59

-0-

0, 39 0 , 78 0, 33 0 , 73 -0- 0 , 05 7th 8th

No'
Holes
at 1OX

maximum

No holes in DX

MIL-F-24385 regulation amendment (June 20, 1974)

25 maximum 25 maximum 10 maximum

Not specified

Not specified Not specified Not specified Not specified

Not a visible one

Pitting

at 10 X Vergroferong

undiluted average of 4 attempts

EXAMPLES 115 through 117

The AFFF agents are prepared with the same ingredients, but in progressively higher concentrations. The data show that stable, high-performance concentrates can be made for 3 percent and even 1 percent dosing. Six percent dosing concentrates such as Aer-O-Water 6 from National Foam or Light Water FC 200 with a solvent content of 18 percent or ~ $ k percent contain so much solvent that they cannot be prepared as 1 percent dosing concentrates.

- 119 609828/1043

cn ο <o

Tabel

Formulation of highly concentrated AFFF agents Example nos, 115 bis

Example no,
Dosing type 115
6% %
Fixed
fabrics -3 116
3 ° / o Fixed
fabrics -7 117
1% Fixed
fabrics -12 R-y amphoteric surfactant Al % like
before
lying 1.00 7.5 % like
before
lying 2.00 7.5 % like
before
lying 6.0 • 7.5 Anion-active R ~ surfactant B2 3.33 0.20 <50 6.66 0.40 <50. 20.0 1.20 <50 Amphoteric auxiliary surfactant Gl2 0.80 1.70 1.60 3.40 4.80 10.20 Non-ionic auxiliary surfactant Dl 1.70 .0.50 3.40 1.00 10.20 3.00 solvent 0.50 - 1.00 - 3.00 - water 6.00 - 12.00 - 36.00 - total 87.67 3.40 75.34 6.80 26.00 20.40 Freezing point ⁰ C 100.00 100.00 100.00 pH Chloride content (ppm)

ro cn on

Claims (1)

PATENT CLAIMS Fluorinated compounds of the formulas N-Q wherein R- straight-chain or branched perfluoroalkyl with 1 to 18 carbon atoms or such perfluoroalkyl substituted by perfluoroalkoxy with 2 to 6 carbon atoms, R branched or straight-chain alkylene with 1 to 12 carbon atoms, alkylenethioalkylene with 2 to 12 carbon atoms, Alkyleneoxyalkylene with 2 to 12 carbon atoms or alkyleneimine alkylene with 2 to 12 carbon atoms, wherein the nitrogen atom contains hydrogen or alkyl having 1 to 6 carbon atoms as a third substituent, y 1 or zero, X is oxygen or -NR-, where R is hydrogen, alkyl having 1 to 6 carbon atoms or hydroxyalkyl having 1 to 6 carbon atoms is, or X together with Q is a piperazine ring - 121 - ο O 9 8 2 ö / 10 4 3 forms, and Q represents a nitrogen-containing group selected from (l) one under R ³ 2 / (la) -I * J ₃ T " R ³ ^ «* 4 and • R (Ic) selected aliphatic amino group in which R for linear or branched alkyl with 2 to 12 carbon atoms, linear or branched alkyl with up to 60 carbon atoms interrupted by oxygen or sulfur or hydroxyl-substituted alkyl, k is 1 or zero, with the proviso that k is 1 when X is oxygen, ■ ζ Λ Rr and R independently of one another each represent hydrogen, one An alkyl or substituted alkyl group having 1 to 20 carbon atoms, a phenyl group, an alkyl or halogen substituted one Phenyl group with 6 to 20 carbon atoms or a polyethoxy or polypropoxy group with 2 to 20 Alkoxy units, with the proviso that R and R are not - 122 609828/1043 Are hydrogen when X is oxygen, and R represents hydrogen, an alkyl group or hydroxyalkyl group, aralkyl or a group of the formula - (CH ₂ ) -COO-alkyl, said alkyl group having 1 to 18 carbon atoms, and G vly among the groups - (CH ₂ J _n -C ₀ A - '(CH ₂ J ₃ SO ₃ O; -CH-C00 © and -c-COO © CH ₂ -COOH cocoon where η is 1 to 5 is selected; (2) under (2a) -R ² - (2b) fr 'and ir (2c) selected cyclic amino groups, in which Υ is a diradical group of the formulas - (CH ₂ ) ₄ -, - (CH ₂ ) ₅ -, - (CH ₂ ) ₂ -0- (CH ₂ ) ₂ - or - (CH ₂ ) -CH-N- (CH ₂ ) ₂ -, wherein R ² , R ⁵ , A ^ and G © have the above- have given meaning, and Y 8 R and R independently hydrogen or a lower alkyl or represent hydroxy-lower alkyl groups having 1 to 6 carbon atoms, with the proviso that R is not hydrogen - 123 609828/1043 MH may be j if X is oxygen j {3) under , 2a (3b) (3c) Za (R ² ) N © A> and selected aromatic amino groups; (4) one under (4a) (4b) and - 124 609828 / 10-4 3 Za ^ - ^ Zb (4c) selected ring-fused amino group in which Z is halogen or methyl and a + b is an integer from 0 to 3 is; and (5) a heterocyclic amino group of the formula (5a) - (R ² ) _k -E (5b) _ (R ² ) _k -E © -R ⁵ ®Ö (5c) - (R ² ) _k -E®-GÖ v / orin k is one or zero and E is substituted by N-hydroxyalkyl or N-aminoalkyl Pyrrolyl, pyrazolyl, imidazolyl, triazolyl, indolyl or indazolyl or ring-substituted by hydroxyalkyl and aminoalkyl Pyridazinyl, pyrimidinyl, pyrazinyl or quinoxalinyl is selected. 2. Compounds according to claim 1 of structures I and II, characterized in that one Q under the constitutions (l) and (2) selects. 3. Compounds according to claim 1 of structures I and II, characterized in that Q under the constructions (la), (2a) and (3a) selects. 4. Compounds according to claim 3, characterized in that 1 2 that R is alkylene, R is straight-chain or branched alkylene 3 4 2 to 5 carbon atoms, y zero, R ^ and R an alkyl group having 1 to 20 carbons or a hydroxyl substituted one - 125 609828/1043 Alkyl group, a polyethoxy group with 2 "to 20 ethoxy units or a group -W R is hydrogen, R is lower alkyl or hydroxyl-substituted Lower alkyl and a represent zero. 5. Compounds according to claim 4, characterized in that that Q- ~ IT R ⁴ 3 4
k is one, R and R independently of one another are alkyl of 1 to 5 carbons, X is oxygen or -NR-, in which R is hydrogen or alkyl of 1 to 3 carbons. 6, connections according to claim 5, characterized in that 1 2 that R ethylene, R straight-chain alkylene with 2 to 5 ■ z L Carbon atoms and R ^ and R represent methyl or ethyl, 7. Compounds according to claim 4, characterized in that Q wherein R is straight-chain alkylene having 2 to 5 carbon atoms is, represents. 8. Compounds according to claim 4, characterized in that * that Q - 126 609828/1043 wherein R is straight-chain alkylene having 2 to 5 carbon atoms, k is 1 and a is zero. 9. Compounds according to claim 1 of the constitution 1 ^ ⁰ R ^ R -S- (CH) -CH- C ^ ^ y ι \ 1 2 where R is alkylene, R is straight-chain or branched Alkylene having 2 to 5 carbon atoms and y is zero and Q has the constitution (la), (2a) or (3a). 10. Compounds according to claim 9, characterized in that Q has the constitutions (1) or (2). 11. Compounds according to claim 1 of the formula I and II, characterized in that Q is chosen from constitutions (Ib), (2b) and (3b). 12. Compounds according to claim 11, characterized in that 1 2 that R is alkylene, R is straight-chain or branched alkylene ■ ζ Λ 2 to 5 carbon atoms, y zero, R ^ and R an alkyl group with 1 to 20 carbons or a hydroxyl-substituted alkyl group, a polyethoxy group with 2 to 20 ethoxy units or a group -N 7 8 R is hydrogen, R is lower alkyl or hydroxyl-substituted Lower alkyl and a represent zero. - 127 609828/1043 13. Compounds according to claim 12, characterized in that that A © under ClO, BrO, CH ₃ CH ₂ OSO ₃ O and CH ₃ OSO ₃ O 5
and R is selected from methyl, ethyl, propyl, butyl and benzyl. 14. Compounds according to claim 1 of the constitution R _f ~ RS _r (CH ₂ ) -CH- C ^ 12 · where R is alkylene, R is straight-chain or branched Alkylene having 2 to 5 carbon atoms and y is zero and Q has the constitution (Ib), (2b) or (3t>). 15. Compounds according to claim 1 of structures I and II, characterized in that Q under the constitutions (ic), (2c) and (3c) is selected. 16. Compounds according to claim 15, characterized in that 1 2 that R is alkylene, R is straight-chain or branched alkylene χ 4 2 to 5 carbon atoms, y zero, R and R an alkyl group with 1 to 20 carbons or a hydroxyl-substituted alkyl group, a polyethoxy group with 2 to 20 ethoxy units or a group _R 3 7 8 R is hydrogen, R is lower alkyl or hydroxyl-substituted Lower alkyl and a represent zero. - 128 809828/1043 17. Compounds according to claim 16, characterized in that G ^ under - (CH ₂ ) 2-COO ^ and - (CH ₂ ) -, SO ^ t) is selected. 18. Compounds according to claim 1 of the constitution -CH C _v 1 2 where R is alkylene, R is straight-chain or branched Alkylene having 2 to 5 carbon atoms and y is zero and Q has the constitution (Ic), (2c) or (3c). 19. Compounds according to claim 1 of the formula C ₀ F ₁ -CII ₀ CH ₀ SCHOc 8 17 2 2 j and its isomer, 20. Compounds according to claim 1 of the formula CH ₂ CONH (CH ₂ ) ₃ KH (CH ₃ ) ₂ and isomers thereof, where R ^ consists of about 25% alkyl groups of 6 carbon atoms, about 50% of alkyl groups of 8 carbon atoms, and about 25% of alkyl groups of 10 carbon atoms. 21. A compound according to claim 1 of the formula - 129 609828/1043 R ,, CH _o CH _o SCHC0CK
£ 2 2 j ^ ₃ CH ₃ and their isomers, where R ~ consists of about 25% of alkyl groups with 6 carbon atoms, about 50% from alkyl groups with 8 carbon atoms and about 25% from alkyl groups with Carbon atoms. 22. Compounds according to claim 1 of the formula R, CH ₀ CH ₀ SCHCOcP CH- £ 22. ι 3 I ' Q CH ₀ CONH (CH ₀ ), -N ^ s _{-CH 0} -COO 2 2 3 .Qb 2. CH ₃ and their isomers, where R- consists of about 25% of alkyl groups with 6 carbon atoms, about 50% from alkyl groups with 8 carbon atoms and about 25% from alkyl groups with Carbon atoms. 23. Compounds according to claim 1 of the formula R-CH ₀ CIi ₀ SCHCOO ⁰ ■ CH TCH ₀ CONH (CH ₀ ), -N- (CH ₀ ) -COG) "2 2 3 j @ 2 CH ₃ and their isomers, where R ~ consists of about 25% of alkyl groups with 6 carbon atoms, about 50% from alkyl groups with 8 carbon atoms and about 25% from alkyl groups with Carbon atoms. - 130 609828/1043 24. Connection. according to claim 1 of the formula CgF ₁₇ C ₂ H ₄ S-CHCOO CH ₀ CONHNH (CK ₀ ) _o 2 3 2 and its isomer * 25. A compound according to claim 1 of the formula CpF CH -S-CHCOO ⁰ CH ₀ CONH (CH) _O NH (C ₀ H) _o and their isomers. 26. A compound according to claim 1 of the formula o X / ^ d 4 ι _ CIi ₂ CONCH ₃ ^ CH ₂ ) NH (CH ₃ ), and their isomers. 27. A compound according to claim 1 of the formula C _n P ₁ -C ₀ H. -S-CHCOO ⁰ 8 17 2 4 j _Θ / ν CH ₀ CONH (CH ₀ ) HN _H
^{2 2 3} \ / and their isomers. 28. A compound according to claim 1 of the formula C ₀ P ₁ -CH, -S-CHCOO® ^{8 17 2 4} I Θ CH ₂ CONH (CH ₂ J ₂ NH (C and their isomers. 29. Compounds according to claim 1 of the formula - 131 609828/1043 ₂ CH ₂ In ¹ H (CH ₃ ) CH ₃ and their isomers, where R ~ consists of about 25% alkyl groups with 6 carbon atoms, about 50% of alkyl groups with 8 carbon atoms and about 25% of alkyl groups with carbon atoms.
30. Compounds according to claim 1 of the formula .CH.CH-S-CHCOO ⁰ NH (CH ₃ ) ^C 2 ^H 5 and isomers thereof, wherein R- consists of about 25% alkyl groups of 6 carbon atoms, about 50% of alkyl groups of 8 carbon atoms, and about 25% of alkyl groups of carbon atoms.
31. A compound according to claim 1 of the formula , NH (CH-J ₉ - and their isomers. 32. A compound according to claim 1 of the formula κ C ₀ F ₁₀ CH ₀ CH ₀ S-CHCOd- - 132 609828/1 043 and its isomer. 33. A compound according to claim 1 of the formula ₀ P,., CH- CH ^ CH ₀ S-CH COO ^ and its isomer. 34. A compound according to claim 1 of the formula C ₀ F, -CH ₀ CH ₀ S-CHCOO " CH ^ COOCH "CH N H and its isomer. 35. Compound ai chosen from the formulas R.-R -S- (CH J-CH-COOII i: * y ι CH ₂ COX - and its isomer or N- wherein L is straight-chain or branched perfluoroalkyl - 133 609828/1043 with 1 to 18 carbon atoms or such by perfluoroalkoxy Perfluoro substituted with 2 to 6 carbon atoms alkyl, R branched or straight-chain alkylene with 1 to 12 carbon atoms, alkylenethioalkylene with 2 to 12 carbon atoms, Alkyleneoxyalkylene with 2 to 12 carbon atoms or alkylene / mlnoalkylene with 2 to 12 carbon atoms, wherein the nitrogen atom contains hydrogen or alkyl having 1 to 6 carbon atoms as a third substituent ^ y 1 or zero, X is oxygen or -NR-, where R is hydrogen, alkyl having 1 to 6 carbon atoms or hydroxyalkyl having 1 to 6 carbon atoms is and T represents a divalent nitrogen-containing group selected from (D (R ² ) - (2) -R ² VTV-R ² - (3) Q
wherein R is an aliphatic hydrocarbon radical having 3 to 19, preferably 3 to 5 carbon atoms. - 134 609828/1043 2559V89 36 »Connection according to claim 35, characterized in that that R is alkylene. 37. Aqueous, film-forming concentrate composition for fire extinguishing or fire prevention by suppressing the evaporation of "flammable liquids, characterized in that that they are out A) 0.5 to 25 % by weight of a fluorinated compound of one of the formulas I to III, B) 0.1 to 5 wt% of an anion-active fluorinated surfactant, C) 0.1 to 25% by weight of an ionogenic non-fluorochemical iensides, D) 0.1 to 40 wt -.% Of a non-ionic non-fluorochemical surfactant, E) 0 to 70 wt .-? 6 solvents as well F) there is enough water to make up the remainder to 100%. 38, composition according to claim 37 »characterized» that the anion-active fluorinated surfactant B) by the formula where R ₊ . is a fluorinated, saturated, monovalent non-aromatic radical with 3 to 20 carbon atoms, the chain carbon atoms only being substituted by fluorine, chlorine or hydrogen atoms with at most one hydrogen or chlorine atom for every two carbon atoms and a divalent oxygen bonded only to carbon atoms or trivalent nitrogen atom in the framework - 135 609828/1043 there may be a chain,
ftf to, where m represents the number 0 or 1, for a multivalent ■
Is a linking group comprising alkylene, sulfonamidoalkylene and carbonamidoalkylene radicals, and Z represents a water-solubilizing polar group comprising anionic radicals; C) the ionic non-fluorochemical surfactant among carboxylic acids, sulfuric acid esters, alkanesulfonic acids, alky! Aromatic Sulfonic acids, phosphates and phosphonic acids, thiosulfates and sulfinic acids; • D) the non-ionic non-fluorochemical surfactant among polyoxyethylene derivatives of alkylphenols, linear or branched alcohols, fatty acids, mercaptans, alkylamines, alkylamides, acetylene glycols, phosphorus compounds, gluco ! I sides, fats and oils, amine oxides and phosphine oxides as well among the surfactants derived from polyoxyethylene and / or polyoxypropylene units containing block polymers is selected and E) the solvent under l-butoxyethoxy-2-propanol, Hexylene glycol and diethylene glycol monobutyl ether is selected, 39. Composition according to claim 38, characterized in that it
A) 1.0 to 3.5 wt -.% Of an amphoteric fluorinated surfactant, j. B) 0.1 to 2.5% by weight of an anion-active fluorinated I surfactants, C) 0.1 to 4.0% by weight of an ionogenic non-fluorochemical - 136 ~ 6 098 2 8/1 0 A 3 Surfactants, D) 0.1 to 8.0% by weight of a non-ionic non-fluorochemical Surfactants and Contains% solvent and enough water to fill up the rest to 100%, - E) 0 to 20 wt. 40. Composition according to claim 39, characterized in that that they A) N- [3- (Dimethylamino) propyl] -2- or -3- (l, l, 2,2-tetrahydroperfluoroalkylthio) succinamic acid, B) a perfluoroalkanoic acid or its potassium salt, C) the partial sodium salt of N-lauryl-ß-iminodipropionic acid, D) Octylphenoxypolyäthoxyäthanol and E) contains l-butoxyethoxy-2-propanol, 41. Composition according to claim 39 _} characterized in that it A) N- [3- (dimethylamino) propyl] -2- or -3- (l, l, 2,2-tetrahydroperfluoroalkylthio) succinamic acid, B) a perfluoroalkanoic acid or its potassium salt, C) the partial sodium salt of N-lauryl-ß-iminodipropionic acid as well as coconut imidazolinium ethosulfate, D) Octylphenoxypolyäthoxyäthanol and E) contains l-butoxyethoxy-2-propanol. 42. Aqueous film-forming composition in aerosol form for extinguishing or preventing fire, characterized in that that it contains the said composition of claim 37 diluted with water and an inert propellant. - 137 -609828/1043 43. Aqueous, forming composition for fire extinguishing or prevention, characterized in that it comprises the said composition diluted with water after Claim 37 contains. 7 " - 138 609828/1043