Note: Descriptions are shown in the official language in which they were submitted.
S3~
The below described invention deals with
novel perfluoroalkyl group containing surfactants.
The importance of the surfactants resides in the
fact that they act as wetting, emulsifying, solu-
bilizing and/or dispersing agents. Although sur-
factants have been prepared from many classes of
compounds, more recently surfactants containing
perfluoro alkyl (Rf) groups have been reported. Rf-
substituted surfactants are especially valuable
because they are known to reduce the surface tension
of liquids more than any other surfactant. For
instance, in water, surface tension of less than 17
dynes/cm can be obtained with fluorinated surfactants,
whereas the non-fluorinated hydrocarbon analogs
reduce the surface tension of water only to about 30
dynes/cm. For this reason the fluorinated surfactants
have found application in such diverse areas as
emulsion-polymerizations, self-polishing floor waxes,
electro-plating, corrosion inhibitors, pains, and fire
fighting compositions.
A variety of fluorinated, amphoteric and cationic
surfactants have been disclosed in U.S. Patent 2,764,602,
3,555,089 and 3,681,413 and in German Offenlegungschrift
2,120,868; 2,127,232; 2,165,057 and 2,315,326. Although
the compounds of the present invention also contain Rf
groups, they are substantially different from the
surfactants disclosed in the above listed patents.
--2--
10~;5;~;~7
Possible intermediates which can be used in
preparing the surfactants of this invention are dis-
closed in U.S. 3,471,518 wherein the addition of Rf-
alkylenethiols to maleic acid and maleates is dis-
closed and U.S. 3,706,787 wherein the addition pro-
ducts of Rf-thiols to dialkyl maleates and monoalkyl
maleates are disclosed. German Offenlegungsschrift
2,219,642 discloses Rf-alkylenethiol addition products
with dialkyl amino-alkyl acrylates and methacrylates,
which compounds are cationic surfactants and do not
possess a 1,2-dicarboxylic moiety. While all fluori-
nated amphoteric surfactants of the prior art are
synthesized by quaternization of an appropriate ter-
tiary amine with an alkylating agent, such as lactones,
sultones or halogenated acids, the amphoteric sur-
factants of this invention are prepared by a simple
ring-opening reaction without the use of potentially
carcinogenic alkylating agents. The surfactants of
this invention are superior wetting agents, especially
when used in combination with other fluorinated and
nonfluorinated surfactants. Furthermore, they can be
manufactured much more economically and safely.
10653Z~
The present invention is directed to novel fluorinated compounds
which are preferably amphoteric or cationic and possess good surface active
properties, and a process for their manufacture. The fluorinated compounds
can be represented by the formulae
Rf-Rl-S-(CH2)y~CH - COOH
CH2- COX-Q
and its isomer
Rf-R -S-(CH2)y~CIH - COX - Q
CH2- COOH II and
,~0
Rf-R -S-(CH2)y~~CH - C -~ Q III
CH2--C~
wherein
Rf is straight or branched chain perfluoroalkyl of 1 to 18 carbon
atoms or said perfluoroalkyl substituted by perfluoroalkoxy of 2 to 6 carbon
atoms,
R is branched or straight chain alkylene of 1 to 12 carbon atoms,
alkylenethioalkylene of 2 to 12 carbon atoms, alkyleneoxyalkylene of 2 to 12
carbon atoms or alkyleneiminoalkylene of 2 to 12 carbon atoms where the
nitrogen atom contains as a third substituent, hydrogen or alkyl of 1 to 6
carbon atoms,
y is 1 or zero,
X i8 oxygen or -NR, wherein R is hydrogen, lower alkyl of 1 to 6
carbon atoms, hydroxyaIkyl of 1 to 6 carbon atoms, or X together with Q forms
a piperazine ring, and
Q is a nitrogen containing group selected from
(1) an aliphatic amino group selected from
(la) / R3
-(R )k-~
R4
_ ~ _
1065327
(lb)
-(R2)k-NR5 A ~
\ R4 and
(lc)
-(R )k-N - G
R4
wherein
R is a linear or branched alkylene of 2 to 12 carbon atoms, oxygen
or sulfur interrupted linear or branched alkylene of up to 60 carbon atoms,
or hydroxyl substituted alkylene. Preferably R2 is a straight chain or
branched alkylene of 2 to 5 carbon atoms;
k is 1 or zero, with the proviso, that if X is oxygen, k is 1,
R3 and R4 are independently of each other hydrogen, alkyl group,
substituted alkyl group of 1 to 20 carbon atoms, phenyl group, a alkyl or
halogen substituted phenyl group of 6 to 20 carbon atoms, polyethoxy or
polypropoxy group of 2 to 20 alkoxy units with the proviso that if X is
oxygen, R3 and R are not hydrogen. The alkyl substituents can be aIkyl of
1 to 5 carbon atoms, dienyl, hydroxyl, carboxyl, halogen, alkylene-
dialkylphosphonate such as methylene-diethylphosphonate or a group
/R3
~ R4
Phenyl subætituents can be methyl, halogen or hydroxyl. Preferably R3 and
R are aIkyl groups of 1 to 4 carbons.
A ~ is any anion which forms an ammonium salt of the formula
0 NH4 A
Anion A ~ is derived from aIkyl halideff, benzene or chlorobenzene
sulfonate esters of alkyl alcohols and methyl and ethyl sulfates. A ~ is
preferably Cl ~ , Br ~ , CH3CH20S03 Q or CH30S03 ~ .
R5 is hydrogen, an alkyl group or hydroxyalkyl group, aralkyl or
groups of the formula -(CH2)n-C00-alkyl, said alkyl group having 1 to 18
carbons. Preferably, R5 is methyl, ethyl, propyl, butyl or benzyl.
1065327
G ~ is a group selected from the groups
-(CH2)n-C00 ~ ; -(CH2)3S03 ~ ;
-CH-C00 ~ and -C-C00
1X2_COOH CH-COOH
where n is 1 to 5;
(2) cyclic amino groups selected from
(2a)
-R2-N Y
(2b) -R2-N ~ A ~ and
(2C) -R2_N Y
G ~
wherein Y is a diradical group of the formulae:
-(CH2)4-
-(CH2)5-
-(CH2)2-0-(CH2)2
-(CH2)-CH-N-(CH2) -
17l8
wherein R , R5, A ~ and G ~ are as defined above,
R7 and R are independently hydrogen, a lower alkyl or hydroxy-
lower alkyl group of 1 to 6 carbon atoms, With the proviso~ that if X is
oxygen, R cannot be hydrogen.
(3) aromatic amino groUps selected from
(3a)
Za
-(R )k
-- 6 --
~0653'X7
(3b)
/Za
-(R )k ~ A
N
15 and
(3c) Za
-(R )k
IN~
G ~
(4) fused-ring aromatic amino group selected from
(4a) Za Zb
-(R )k ~
(4b) Za Zb
-(R )k ~ A
I
R5 and
(4c) Za Zb
~R2 )k
wherein
Z is halogen or methyl,
a + b is an integer from 0-3; and
(5) a heterocyclic amino group o~ the formula
(5a) -(R2)k-E
(5b) -(R2)k-E ~ -R5 A
-- 7 --
iO653~7
(5c) -(R2)k-E ~ -G
where k is one or æero and
E is selected from N-hydroxyalkyl or N-aminoalkyl, substituted
pyrrole, pyrazole, imidazole, triazole, indole or indazole, hydroxyaIkyl and
aminoalkyl ring-substituted pyridazine, pyrimidino, pyrazino or quin-
oxalino.
The present invention is further directed to aqueous film forming
concentrate compositions for extinguishing or preventing fires by suppressing
the vaporization of flammable liquids and to a process for fighting (extin-
guishing or preventing) fires uherein these compositions are used.
The compounds represented above by formulae I and II where Q is ofstructures (la), (2a), (3a), (4a) or (5a) exist in solution in the form of
their inner salts, having the general structures
Rf-R -S-(CH2)y~fH~ COO Ia
CH2 - COX-QH and
Rf-R ~S(CH2)y~fH - COX-OH IIa
CH2-COO ~)
and thus are amphoteric surfactants.
The compounds of structure III are obtained through imidization of
compounds of structures I and II, when X is -NH- by heating, either in bulk
or in solution, to a temperature range of from 50 to 150C or preferably to
a temperature of about 100 C. The compounds of this invention uhere Q is of
structures (la), (2a), (3a~, (4a) or (5a) are prepared from mPleic or
itaconlc anhydrides, perfluoroalkyl group-containing thiols and a polyamine
or an aminoalcohol. Typically, they are prepared in two steps: first,
maleic anhydride or itaconic anhydride is reacted uith an equimolQr amount
of either an alcohol containing at least one tertiary amino group, or a
primary or secondary amine containing at least one more primQry, secondary
or tertiary amino group, to form an unsaturated intermediate half ester or
half amide of structures:
-- 8 --
10653Z7
/coo 9
HC or
HC
COX-QH
H2C=CH-COO ~)
CH2-COX-QH
where x is defined as above and Q is of structures (la), (2a), (3a), (4a) or
(5a).
Compounds of this structure are described in the literature as
comonomers for vinyl polymerization. For instance,
8H-COO ~
CH-CNX(CH2)3~(CH3)2
N-(3-dimethylaminopropyl)maleic acid amide, in United States 2,821,521.
For compounds in which X is -N-CH3 or -N-C2H5 and Q is
-CH2CH2-N(CH3)2 the intermediate undergoes cyclization and forms a compound
of structure:
H3C CX3
\~/
N ~ CH2COO
~ - o
I
CH3 (or -C2H5)
These compounds are new and their structures have been confirmed by
~MR and by the absence of an acidic hydrogen.
Instead of preparing the intermediate from the anhydride by ring
opening, other synthesis routes can be used; as for instance, transesterifica-
tion or transamidification of a lower alkyl maleic, fumaric or itaconic half
ester.
Synthesis of the novel surfactants is completed in a second reaction
10653;~7
step during which the perfluoroalkyl substituted thiol is added to the double
bond of the intermediate by base catalysis. This reaction normally proceeds
at room temperature, except where an intermediate of the above described
cyclic type is formed; in this case addition of the thiol occurs only at
temperatures of 85 C and above.
Alternately, the synthetic route can be reversed and the Rf-thiol
added to the unsaturated, cyclic anhydride or its lower aIkyl monoester
through base-catalysis or by a free-radical mechanism. The intermediate is
then reacted with an alcohol containing at least one tertiary amino group or
a primary or secondary amine containing at least one more primary, secondary
or tertiary amino group which yields the desired product. The first synthesis
route is preferred because of the high yield and purity of the product.
The mono-esters can be easily synthesized by reacting an equimolar
amount of an unsaturated cyclic anhydride and the amino alcohol, either in
bulk or in solution. The mono-amides can be prepared by reacting at a tem-
perature below 50 C in a solvent equimolar amounts of an unsaturated cyclic
anhydride with a polyamine. The useful solvents are such as methyl-ethyl
ketone, diethylene glycol dimethylether, dimethylformamide, tetrahydrofuran,
perchloroethylene, l,l,l-trichloroethane, dichloromethane, dioxane, dimethyl-
sulfoxide, ~-methyl pyrrolidone. The amides can also be prepared in water
or a mixture of water and an above listed solvent by adding the anhydride to
the aqueous solution of the amine as described in greater detail in Canadian
Patent 828,195.
The Rf-substituted thiol addition to the mono-esters and mono-
amides i9 carried out in solution or in bulk at a temperature between 20 to
100 C. Useful solvents are alcohols such as methanol, ethanol, n-propanol,
isopropanol, n- and isobutanol, amyl alcohol, n-hexanol, cyclohexane, benzyl
alcohol and the like; ethers such as dimethyl ether, methyl ethyl ether,
diethyl ether, di-n-propyl ether, diisopropyl ether, methyl n-butyl ether,
ethyl n-butyl ether, ethylene glycol dimethyl ether, divinyl ether, diallyl
ether, tetrahydrofuran and the like; ketones such as acetone, methyl ethyl
ketone, methyl n-propyl ketone, diethyl ketone, hexanone-2, hexancne-3,
_ 10_
10653Z7
methyl t-butyl ketone, di-n-propyl ketone, diisopropyl ketone, diisobutyl
ketone, chloroacetone, diacetyl, acetyl acetone, mesityl oxide, cyclohexanone
and t.1e like; N-methyl pyrrolidone, dimethylformamide, acetonitrile, benzene,
chlorob-nzene, chloroform, methylenechloride, carbontetrachloride, dioxane,
nitrobenzene, toluene and the like. Water can also be employed or a mixture
of water and any one of the preceding solvents.
Preferred are solvent mixtures containing methanol, eth~nol, iso-
propanol, carbitol or butylcarbitol, or water. If for a subsequent reaction,
for instance quaternization with propanesultone, the alcohol has to be re-
moved, a mixture of N-methylpyrrolidone and a low boiling alcohol such as
methanol is preferred. Since the maleic mono-esters or maleic mono-amides
already contain an amino group, no additional amine has to be added to
catalyze the thiol addition.
The novel surfactants thus obtained are directly soluble in water
or water/co-solvent mixtures. The solutions are essentially neutral. In
dilute aqueous solution the tert-aminoalkyl mono-esters and mono-amides form
polymeric aggregates leading to very high viscosities; these gel-type solu-
tions are easily broken up by addition of a co-solvent, such as butylcarbitol,
or a nonionic co-surfactant, such as an ethoxylated alkyl-phenol.
The compounds of this invention where Q is of structures (lb and c),
(2b and c), (3b and c), (4b and c) and (5b and c) are prepared by quaterniza-
tion of the amphoteric surfactants prepared as described above.
The quaternization reaction can be carried out in the presence or
absence of an inert solvent. Suitable solvents are diethyl ether, aceton-
itrile, dimethylformamide, N-methylpyrrolidone and the like.
The temperature of the reaction is not critical and may range from
0C to about 150 C depending on the reactivity of the quaternizing agent.
The resultant quaternary ammonium co~pounds are frequently obtained
as solids when an inert solvent is employed. They can be readily separated,
washed and dried. The products can be isolated from solution by addition of
a nonsolvent, as will be kno~n to one skilled in the art. The products can
be further purified if desired by recrystallization from an appropriate sol-
-- 11--
~0653;~7
vent or solvent mixture. Produets obtained as viseous liquids can be further
purified by extraction with a suitable solvent.
If the amino aleohol is a diol or a polyamine whieh contains at
least three am-no groups at least two of whieh are primary or seeondary amino
groups, it ean be reacted with two moles of maleic or itaconic anhydride and
two moles of Rf-alkylenethiol yielding bis-R~-alkylenethiosuccinic acid half-
amides, half-esters and suecinimides whieh ean be represented by the formulae
r f ( 2)y 1 1
L CH2COX~T
and its isomer or
~Rf-R -S- ( CH2 )y~ I -C~
l H2C-C~
wherein T is a nitrogen eontaining divalent group seleeted from
R3
(1) R2 N /
(R2)_
(2) -R2-N N ~-R2-
(3) -Rl9 ~ N
where R is an aliphatie hydro-earbon triradieal of 3 to 10 earbon atoms,
preferably of 3 to 5 earbons. An example of strueture (3) is the 3-pyridyl-
pentane 1,5-diradieal.
If in struetures I and II X is oxygen, Q is derived from tert-amino
group eontaining aleohols of the formula
(1) / R3
\ R4
iO653;~7
where R3 and R4 are as defined above.
Illustrative examples of the above represented alcohols are
H0-CH2-CX2-N(CH3)2
2 2 (C2H5)2
2 3 ( 3)2
HO-(CH2)3-N(C2H5)2
H0-(CH2)3-N(c3 7)2
HO-(CH2)4-N(cH3)2
HO-(CH2)5-~(CH3)2
H-(CH2)6-N(CH3)2
( 2)8 ( 3)2
HO(CH2)10-N(CH3)2
HO(CH2)12-N(CH3)2
H0-CH-fH2N(CH3)2
CH3
ICH3
Ho-(cH2cH2o)xcH2cH2-N-(cH2) (CH2 2 Y
where x ~ y = 3-25 and z = 1-20
HO-CH2CH2-N(phenyl)CH2CH20H
H0-CH2CH2-N(tolyl) CH2CH20H
Ho-fH-cH2-N(phenyl)cH2fH-oH
CH3 CH3
HOCH2CH2-N-CH2 CH20H
/ ~OC2H5
CH2-P=O
2 5
Another class of tert-amino containing alcohols are cyclic compounds
of the formula
(2) HO_R
where
R and Y are as defined above.
~ 13 ~
10653'~7
Illustrative examples of the above represented alcohols are
2)2
HO(CH2)2 N 3
HO(CH2)2 N ~ O
HO(CH2)3-- H ~-~CH2)3
CH3
Still other classes of tert-amino group containing alcohols are of
the formulae
(3) ~a
Ho-R2_~3
N or
t4) Zb Za
HO-R
or
(5) HO(R )k-E
wherein R , Z, E, a, b and k are as defined above.
Illustrative examples of such alcohols are
2-, 3- and 4-(2'-hydroxyethyl)pyridine
3-methyl-4-(2'-hyaroxyethyl)pyridine
2-methyl-4-(2'-hydroxyethyl)pyridine
2-, 3-, 4-, 5-, 6-, 7-, and 8-(2'-hydroxyethyl)quinolines
3-pyridyl-1,5-pentane diol.
When in formulae I or II X is -~R, such a moiety can be derived
-14 -
1065327
from a primary or secondary a~ine containing at least one other amino group.
Such amines can be represented by the formula
(1) / R3
HN-(R )k-N
\ R
where
R to R and k are as defined above.
Illustrative examples of the above represented amines are
NH2(CH2)2N(cx3)2
NH2(CH2)2~(c4H9)2
CH3NH(CH2)2N(CH3)2
Ii~H2(CH2)3N(c3H7)2
NH2(CH2)4N(c2H5)2
NH2(CH2)5N(C2H3)2
NH2(CH2)ôN(c3H7)2
NH2(CH2)2N(C2H5)2
NH2(CH2)3N(CH3)2
CH3NH(CH2)2N(C2H3)2
NH2(CH2)3N(c4H9)2
CH3NH(cH2)4N(cH3)2
NH2(C~2)6~(C2H5)2
NH2(CH2)8~(c4H9)2
2( 2)2 (C3 7)2
NH3(CH2)3N(c2H5)2
C2H5NH(CH2)2N(c2H5)2
H2( H2)4 (CH3)2
NH2(CH2)5N(cH3)2
NH2(CH2)6N(C3H7)2
NH2(CH2)10N(C3H7)2
NH2(CH2)l2N(c3H7)2
CH3NH(CH2)3N(CH3)2
H2N(CH2)2N(CH2CH20H)2 ~ 15 -
10653Z7
i
H2N-N(CH3)2
CX3NH-N(CH3)2
2 2 H2CH2NHCH3
H2NCH2CH2NHCH3
H2I~CH2CH2CH2NH2
H2NCH2CH2N~2
H2NcH2cH2cH2N(cH3)cH2cH2cH2NH2
H2NcH2cH2NHcH2cH2oH .
Another class of primary and secondary amines containing at least
one other amino group are heterocyclic compounds of the formulae
(2)
HN-(R2)-M ~ y or
R
~ 5
HN H N-R
wherein
R, R , R5 and Y are as defined above.
Illustrative examples of the amines above are
N-(2'-aminoethyl)piperidine
N-(2'-aminoethyl)morpholine
N-(4'-aminobutyl)piperidine
N-(2'-aminoethyl)-pyrrolidine
N-methyl piperazine
piperazine
N-(2-hydroxyethyl)piperazine.
Still other classes of primary and ~econdary amines containing at
least one other amino group are aromatic heterocyclic compounds containing
five and six membered ringæ. These classes include
_ 16 _
~f)653Z7
(3) (4)
Za Zb Za
H-l-(CH2)V ~ H~
and
(5)H2N(R )k-E
wherein
R, R2, Z, E, a and b are as defined above, and
v is an integer of from 0 to 12.
Illustrative examples of the amines represented above are
2-aminomethylpyridine
2-(2'-aminoethyl)pyridine
3-(2'-aminoethyl)pyridine
3-aminomethylpyridine
2,6-dichloro-3-aminomethylpyridine
2-methyl-3-(2'-Qminoethyl)pyridine
3-(4'-aminobutyl)pyridine
4-~minomethylpyridine
4-(2'-aminoethyl)pyridine
2-aminopyridine
3, 4, 5 or 6-methyl-2-aminopyridines
3, 4, 5 or 6-chloro-2-aminopyridines
203-aminopyridine
2-chloro-6-methyl-3-aminopyridine
4-aminopyridine
dichloro-4-aminopyridines
2-aminopyrimidine
2-, 3-, 4-, 5-, 6-, 7- and 8-(4'-amino-butyl)quinolines
2-, 3-, 4-, 5-, 6-, 7- and 8-(3'-methy~minopropyl)quinolines
2, 3, 4, 5, 6, 7 or 8-aminoquinolines
chloroaminoquinolines
-17 -
1065327
methylaminoquinolines
guanine
adenine.
Compounds having structures I, II or III, where Q is of structure
(lb), (2b), (3b) or (4b) are derived from the corresponding amines by
quaternization with compounds of the structure
R5A
where R5 and A are as defined above.
Suitable compounds of the fo~mula R5A are those in which R5 is an
alkyl group of 1 to 18 carbon atoms and A is any anion which forms an
ammonium salt of the formula ~H4+A having a solubility in water of at least
about 1%. Useful examples of R5A are the methyl-, ethyl-, propyl-, iso-
propyl-, butyl-, isobutyl-, sec-butyl-, hexyl-, octyl-, ethylhexyl-, decyl-,
dodecyl-, tetradecyl-, hexadecyl-octadecyl-chlorides, bromides and iodides;
benzylchloride; halo-alkanoic acid esters, and halo alkyl-alkyl ethers.
The normal alkyl halides, i.e., n-propyl, n-butyl, n-octyl or r,-
hexadecyl, are preferred. Also useful are the toluene, benzene and chloro-
benzene sulfonate esters of methyl, ethyl, propyl, butyl and like alcohols,
and methyl and ethyl sulfate. When methyl or ethyl sulfate (R2S04) is used,
the anion A in the product of the present invention will usually be a mixture
of RS04- and
~04 ~fRS(CH2)yCHCOOH
L CH2COX-Q _¦ ~
Also useful are mineral acids, such as HCl, HBr, HI, H3P04 and H2S04, and
organic acids, such as acetic, formic, acrylic acids.
The compounds of structures I, II and III where Q is of structure
(lc), (2c), (3c), (4c) or (5c) are similarly derived from the corresponding
amines by quaternization with
(a) Hal-R6-COOH
wherein Hal stands for chlorine, bromine or iodine,
~ 18 ~
iO65327
R6 is an alkylene group of 1 to 5 carbon atoms, or a group
-CH- -C-
11
CH2COOH CH-COOH ,
(b) R O-CHCH2CO or
o
~-lactones
( c ) CIH2CH2-S02
CH2 0
propane sultone
wherein R is hydrogen or an aIkyl group of 1 to 6 carbon atoms.
The perfluoroalkyl thiols employed in the preparation of the com-
poundæ of this invention are well kno~n in the prior art. For example, thiols
of the formula RfRl-SH have been described in a number Or United States
patents including 2,ô94,ggl; 2,961,470; 2,965,677; 3,088,849; 3,172,190;
3,544,663 and 3,655,732.
Thus, IJnited States Patent 3,655,732 discloses mercaptans of for-
mula
Rf-R -SH
where
R is alkylene of 1 to 16 carbon atoms and Rf is perfluoroalkyl and
teaches that halides of formula Rf-R -hal are well known; reaction of RfI with
ethylene under free-radical conditions gives Rf(CH2CH2)aI while reaction of
RfCH2I with ethylene gives RfCH2(CH2CH2)aI as is further taught in United
States Patents 3,o88,849; 3,145,222; 2,965,659 and 2,972,638.
United States Patent 3,655,732 ~urther discloses compounds of for-
mula
R~-R'-X-R"-SH
where
R' and R" are alkylene of 1 to 16 carbon atoms, with the sum Or the
carbon atoms of R' and R" being no greater than 25; Rf is perfluoroalkyl of 4
through 14 carbon atoms and X is -S- or -NR "'- where R " ' is hydrogen or
19
~0~53,f~7
alkyl of 1 through 4 carbon atoms.
United States Patent 3,544,663 teaches that the mercaptan
RfCH2CH2SH
where
Rf iB perfluoroalkyl of 5 to 13 carbon atoms, can be prepared by
reacting the perfluoroaIkyl alkylene iodide with thiourea or by adding H2S
to a perfluoroalkyl substituted ethylene (Rf-CH=CH2), which in turn can be
prepared by dehydrohalogenation of the halide Rf-CH2CH2-hal.
The reaction of the iodide Rf-R -I with thiourea followed by
hydrolysis to obtain the mercaptan Rf-R -SH is the preferred synthetic route.
The reaction is applicable to both linear and branched chain iodides. Many
useful per n uoroalkoxyalkyl iodides are described in United States Patent
3,514,437 of general formula
(CF3)2CF0 CF2CF2(CH2CH2)m
where
m is 1-3.
Particularly preferred herein are the thiols of formula
RfCH2CH2SH
where
Rf is perfluoroalkyl of 6 to 12 carbon atoms. These Rf-thiols can
be prepared from RfCH2CH2I and thiourea in very high yield.
Illustrative examples of preferred perfluoroalkylalkylenethiols are
C4F9 H2CH2 H
C6F13CH2CH2SH
C8F17CH2CH2SH
CloF21CH2CH2SH
C12F25CH2CH2SH
CF3
\ CF0(CF2CF2)l to 3 CH2CH2
CF3
Especially preferred perfluoroalkylalkylenethiols are
- 20 -
10653Z~
t
C6F13CH2CH2SH
C8F17CH2CH2SH
CloF21CH2CH2SH
and mixtures thereof.
Unsaturated dicarboxylic cyclic anhydrides which can be employed in
preparing the surfactants of this invention can be amleic and a~kyl and
halogen substituted maleic ~nhydrides such as citraconic and chloro and
dichloromaleic anhydrides. Preferred are itaconic and maleic and most pre-
ferred maleic anhydride.
The compounds of this invention, as noted above, are effective
surfact~nts and therefore can be employed in all applications where
surfactants are required. These surfactants would be employed as prior
art surfactants which is self evident to those skilled in the art. Specific
examples where the instant surfactant can be employed are as wetting agents
in coatings, waxes, emulsions, paints. They are especially useful when for-
mulated with other nonfluorinated surfactants as fire fighting agents. A
particular advantage of these surfactants is their low toxicity to aquatic
life.
A particular advantage of the compounds of this invention where Q
is represented by structures (la), (2a), (3a), (4a) and (5a) is that they are
amphoteric surfactants made without a specific quaternization reaction step
which require the use of carcinogenic alkylating agents such as ~-lactones
and propane sultones. The prior art amphoteric surfactants require such
quaternization step. The compounds of this invention are particularly useful
in the preparation of aqueous fire fighting formulations, especially when
used in combination with non-fluorinated surfactants. Such formulations have
superior hydrocarbon fire fighting properties.
Preferred surfactants of this invention are the amphoteric
surfactants of formulae Ia and IIa where Q is of structures (la), (2a) or
(3a). More preferred are those where Rf is linear perfluoroalkyl of 6 to 12
carbon atoms, R is ethylene and y is zero. The most preferred surfactants
are those where X is ~R and Q is of structure (la) where R is a straight
_ 21 _
10653Z7
chain alkylene of 2 to 5 carbon atoms, R is hydrogen, methyl or ethyl and R3
and R4 are methyl or ethyl.
It is also well-known that synergistic surface tension effects are
achieved from mixtures of different types of Rf-surfactants, as for instance
nonionic and anionic Rf-surfactants, alone or in combination with classical
hydrocarbon co-surfactants as told by ~ernett and Zisman (J. Phys. Chem. 65,
448, (1961) ) .
Tuve et al in United States 3,258,423 also disclose the use of
aqueous solutions of certain Rf-surfactants or Rf-surfactant mixtures alone
or in combination with solvents and other additives as efficient fire fight-
ing agents. Based on the Tuve et al findings many other fire fighting agents
containing different Rf-surfactant systems have been disclosed as shown in
United States 3,315,326 and 3,772,195.
Fire fighting agents containing Rf-surfactants act in two ways:
a. As foams, they are used as primary fire extinguishing agents.
b. As vapor sealants, they prevent the re-ignition of fuels and
solvents.
It is this second property which makes fluorochemical fire fighting
agents far superior to any other known fire fighting agent.
These Rf-surfactant fire fighting agents are commonly known as AFFF
(standing for Aqueous Film Forming Foams~. AFFF agents act the way they do
because the Rf-surfactants reduce the surface tension of aqueous solutions
to such a degree that the solutions will wet and spread upon non-polar and
water immiscible solvents even though such solvents are lighter than water;
they form a fuel or solvent vapor barrier which will rapidly extinguish
flames and prevent re-ignition and reflash. The criterion necessary to attain
spontaneous spreading of two immiscible phases has been taught by Harkins et
al, J. Am. Chem. 44, 2665 (1922). The measure of the tendency for spontaneous
spreading is defined by the spreading coefficient (SC) as follows:
sc = ya - yb - yi
where SC = spreading coefficient
ya - surface tension of the lower liquid phase
10653Z~7
yb = surface tension of the upper aqueous phase
yi = interfacial tension between the aqueous upper phase and lower
liquid phase.
If the SC i8 positive, the surfactant solution should spread and film forma-
tion should occur. The greater the SC, the greater the spreading tende~cy.
This requires the lowest possible aqueous surface tension and lo~est inter-
facial tension, as is achieved with mixtures of certain Rf-surfactant(s) and
classical hydrocarbon surfactant mixtures.
Commercial AFFF agents are primarily used today in so-called 6% and
3% proportioning systems. ~% means that 6 parts of an AFFF agent and 9~
parts of water (fresh, sea, or brackish water) are mixed or proportioned and
applied by conventional foam making equipment wherever needed. Similarly
an AFFF agent for 3% proportioning is mixed in such a way that 3 parts of this
agent and 9~ parts of water are mixed and applied.
Today AFFF agents are used wherever the danger of fuel solvent
fires exist and especially where expensive equipment has to be protected.
They can be applied in many ways, generally using conventional portable
handline foam nozzles, but also by other techniques such as with oscillating
turret foam nozzles, subsurface in~ection equipment (petroleum tank farms),
fixed non-aspirating sprinkler systems (chemical process areas, refineries,),
underwing and overhead hangar deluge systems, inline proportioning systems
(induction metering devices), or aerosol type dispensing units as might be
used in a home or vehicle. AFFF agents are recommended fire suppressants for
Class A fires such as fires of wood, cloth, paper, rubber or plastics or
Class B fires, such as fires of flammable solvents, gasoline, gases or
greases particularly the latter. Properly used alone or in con~unction with
dry chemical extinguishing agents (twin-systems) they generate a vapor-
blanketing foam with remarkable securing action.
AFFF agents generally have set a new standard in the fighting of
fuel fires and surpass by far any performance of the previously used protein
foams. However, the performance of today's commercial AFFF agents is not
the ultimate as desired by the industry. The very high cost of AFFF agents
- 23 -
10653Z7
is limiting a wider use and it is, therefore, mandatory that more efficientAFFF agents which require less fluorochemicals to achieve the same effect
are developed. Furthermore, it is essential that secondary properties of
presently available AFFF agents be improved. The new AFFF agents should
have: a) a lower degree of toxicity (fish toxicity is a very essential
element whenever AFFF agents are dispensed in large quantities and when there
is a chance that such agents might pollute receiving streams and lakes; this
is a ma~or problem on test grounds where AFFF agents are often used); b) a
lower chemical oxygen demand (COD); good biodegradability (so as not to hin-
der the activity of microorganisms in biological treatment systems); c) aless corrosive character so that they can be used in light weight containers
made of aluminum rather than heavy, non-corrosive alloys; d) improved long
term storage stability; e) good compatibility properties with conventional
dry chemical extinguishers; f) an improved vapor sealing characteristic and
seal speed, and most importantly; g) have such a high efficiency that instead
of using 3 and 6% proportioning systems it might become possible to use AFFF
agents in 1% or lower proportioning systems. This means that 1 part of an
AFTF agent can be blended or diluted with 99 parts of water. Such highly
efficient concentrates are of importance because storage requirements of AFFF
agents will be greatly reduced, or in the case where storage facilities exist~
the capacity of available fire protection agent will be greatly ~ncreased.
AFFF agents for 1% proportioning systems are of great importance therefore
wherever storage capacity is limited such as on offshore oil drilling rigs,
offshore atomic power stations, city fire trucks and so on. The performance
expected from an AFFF agent today is in most countries regulated (for example
United States Navy Military Specification MIL-F-24385 and its subsequent
amendments).
The novel AFFF agents described of this invention are in comparison
with today's AFFF agents superior not only with regard to the primary per-
formance characteristics such as control time, extinguishing time and burn-
back resistance but additionally, because of their ~ery high efficiency offer
the possibility of being used in 1% proportioning systems. Furthermore, they
- 24 -
10653Z7
offer desirable secondary properties from the standpoint of ecology as wellas economy.
As indicated above the present invention is further directed to
aqueous film forming concentrate compositions for extinguishing or preventing
fires by suppressing the vaporization of flammable liquids, said composition
comprising
A) 0.5 to 25% by weight of a fluorinated compound (surfactant), of any of
the formulae I to III,
B) 0.1 to 5% by weight of anionic fluorinated surfactant,
C) 0.1 to 25% by weight of ionic non-fluorochemical surfactant.
D) 0.1 to 40% by weight of nonionic non-fluorochemical surfactant,
E) 0 to 70g by weight of solvents, and
F) water in the amount to make up the balance of 100%.
To form effective compositions, a mixture of various surfactants
must attain surface tensions of less than about 26 dynes/cm. Each component
(A) to (E) may consist of a specific compound or a mixture of compounds.
The above composition is a concentrate which, as noted above, uhen
diluted with water, forms a very effective fire fighting formulation by form-
ing a foam which deposits a tough film over the surface of the flammable
li~uid which prevents its further vaporization and this extinguishes the
fire.
It i8 a preferred fire extinguishing agent for flammable solvent
fires, particularly for hydrocarbons and polar solvents of low water solu-
bility, in particular for:
Hydrocarbon Fuels - such as gasoline, heptane, toluene, hexane, Avgas*, VMP
naphtha, cyclohexane, turpentine, and benzene;
_olar Solvents of Low Water Solubility - such as butyl acetate, methyl iso-
butyl ketone, butanol, ethyl acetate, and
Polar Solvents of High Water Solubility - such as methanol, acetone, iso-
propanol, methyl ethyl ketone, ethyl cellosolve and the like.
It may be used concomitantly or successively with flame suppressingdry chemical powders such as sodium or potassium bicarbonate, ammonium
*Trademark - 25 -
10~53Z7
dihydrogen phosphate, C02 gas under pressure, or Purple K, as in so-called
Twin-agent systems. A dry chemical to AFFF agent ratio would be from 4,5 to
13,6 kg of dry chemical to 7,5 to 37,853 1 AFFF agent in use concentration
(i.e. after 0.5%, 1%, 3%, 6% or 12% proportioning). In a typical example
9 kg of a dry chemical and 18,9 1 of AFFT agent could be used. The com-
position of this invention could also be used in con3unction with hydrolyzed
protein or fluoroprotein foams.
The foams of the instant invention do not disintegrate or otherwise
adversely react with a dry powder such as Purple-K Powder ~P-K-P). Purple-K
Powder is a term used to designate a potassium bicarbonate fire extinguishing
agent which is free-flowing and easily sprayed as a pouder cloud on flammable
liquid and other fires.
The concentrate is normally diluted with water by using a propor-
tioning system such as, for example, a 3% or 6~ proportioning system whereby
3 parts or 6 parts of the concentrate is admixed with 97 or 94 parts respec-
tively of water. This highly diluted aqueous composition is then used to
extinguish and secure the fire.
Component (B) is a fluorinated anionic surfactant. The exact
structure of these surfactants is not critical and they may be chosen from
compositions wherein the fluoroaliphatic surfactant is a water soluble
fluoroaliphatic compound represented by the formula
RfQmZ
wherein
Rf is a fluorinated saturated monovalent non-aromatic radical con-
taining from 3 to 20 carbon atoms in which the carbon atoms of the chain are
substituted only by fluorine, chlorine or hydrogen atoms with no more than
one hydrogen or chlorine atom for every two carbon atoms, and in which a
divalent oxygen or tri~alent nitrogen atom, bonded only to carbon atoms, can
be present in the skeletal chain;
~ , where m is an integer of 0 or 1, is a multivalent linking group
comprising alkylene, sulfonamido alkylene and carbonamido alkylene radicals;
and Z is a water solubilizing polar group comprising anionic radicals.
-26 -
10653Z 7
Preferred anionic groups are -C02 and -S03 . The anionic
surfactant should contain 30-65% of carbon bound fluorine in oraer to attain
suitable solubility properties. The anionic surfactant may be present as
free acid, an aIkali metal salt thereof, = onium, or substituted ammonium.
Illustrative exa~ples of Rf-anionics which can be used in the com-
positions of this invention are the below shown acids and their alkali metal
salts. The patent numbers appearing in parenthesis are patents which more
fl~lly disclose the represented class of compounds.
Carboxylic Acids and Salts thereof
RfCOOH (Scholberg et al, J. Phys. Chem,
57, 923-5(1953)
ft 2)1-20 (Ger. 1,916,669)
RfO(CF2)2 20COOH (Ger. 2,132,164)
RfO(CF2)2_20(cH2)2-2o (Ger. 2,132,164)
RfO(CH2)1 20COOH (U.S. 3,409,647)
RfS02N(C2H5)CH2COOH (U.S. 3,258,423)
RfO(CF20)3CF2COOH (Fr. 1,531,902)
RfO (CF2CIFO\ CF2COOH (Fr. 1,537,922)
\ CF3/3
RfO[CF(CF3)CF20]CF(CF3)CON(CH3)CH2COOH
(U.S. 3,798,265)
(C2F5)2(CF3)CCE2COOH (Brit. 1,176,4g3)
CloFlgOC6H4CON(CH3)CH2COOH (Brit. 1,270,662)
Rf(CH2)1 3SCH(COOH)CH2COOH ~U.S. 3,706,787)
Rf(CH2)1 12s(cH2)l 17COOH Ger. 2,239,709; U.S. 3,172,900
Sulfonic Acids and Salts Thereof
RfS03H (U.S. 3,475,333)
RfC6H4S03H (Ger. 2,134,973)
f( 2)1-20 3 (Ger. 2,309,365)
f 2 H 2C6 4 03 (Ger. 2,315,326)
RfS02N(cH3)(c2H40)l-2o 3 (S.A. 693,583)
RfCH2CH20CH2CH2CH2S03H (Can. 842,252)
RfOC6H4S03H (Ger 2;230,366)
106532'7
C12F230C6H4S03H (Ger. 2,240,263)
(C2F5)3CO(CH2)3S03H (Brit. 1,153,854)
CF3(C2F5)2CO(CH2)3S03H (Brit. 1,153,854)
(c2F5)2(cF3)ccH=c(cF3)so3H (Brit. 1,206,596)
RfOCF(CF3)CF20CF(CF3)CONHCH2S03H (U.S. 3,798,265)
PhosphQnates, Phoæphates, Related Phosphoro Derivatives,
and Salts Thereof
RfPO(OH)2 (Rf)2PO(OH) (Ger. 2,110,767)
PfS2N(Et)C2H4PO(OH)2 (Ger. 2,125,836)
RfCH20PO(OH)2 (Ger. 2,158,661)
C8F150c6H4cH2Po(OH)2 (Ger. 2,215,387)
RfOC6H4CH2PO(OH)2 (Ger. 2,230,366)
Others (and Salts Thereof)
RfS02N(CH3)C2~40S03H (Ger. 1,621,107)
RfC6H40H (U.S. 3,475,333~
Rf(CH2)1_20S23Na (Ger. 2,115,139)
f( 2)1~20so2N(cH3)cH2cH2s2o3~a (Ger. 2,115,139)
RfS02H (U.S. 3,562,156)
In the sulfonate class of the fluorinated anionic surfactant~ a
particularly preferred type of compounds are sulfonates formed by the reac-
tion of 1,3-propane sultone and a perfluoroalkylthiol and have the structure
Rf-R -S- ( CH2 ) 3S03 ~) Z ~
wherein Rf and Z are aæ defined above and R is as defined below.
The perfluoroaIkyl thiols employed in the preparation of the
sultones are well known in the prior art. For example, thiols of the formula
RfR -SH have been described in a number of United States patents including
2,894,991; 2,961,470; 2,965,677; 3,o88,849; 3,172,190; 3,544,663 and
3,655,732.
Thus, United States Patent 3,655, 732 discloses mercaptans of for-
mula
R~_Rl_SH
where
_ 28 _
lQ653Z7
Rl is alkylene of 1 to 16 carbon atoLs and Rf is perfluoroalkyl
and teaches that halides of formula Rf-R -hal are well known; reaction of
RfI with ethylene under free-radical conditions gives Rf(CH2CH2)aI while
reaction of RfCH2I with ethylene gives RfCH2(CH2CH2)aI as is further taught
in United States Patents 3,o88,849; 3,145,222; 2,965,659 and 2,972,638.
United States Patent 3,655,732 further discloses compounds of for-
mula
Rf-Rl-x-R~-sH
where
R and R" are alkylene of 1 to 16 carbon atoms, with the sum of
the carbon atoms of Rl and R" being no greater than 25; Rf is perfluoroalkyl
of 4 through 14 carbon atoms and X is -S- or -~R " '- where R " ' is hydrogen
or alkyl of 1 through 4 carbon atoms.
The reaction of the iodide Rf-Rl-I with thiourea followed by
hydrolysis to obtain the mercaptan Rf-R -SH i6 the preferred synthetic route.
The reaction is applicable to both linear and branched chain iodides. Many
uæeful perfluoroalkoxyalkyl iodides are described in United States Patent
3 514 487, of general formula:
(CF3)2CF0 CF2CF2(CH2CH2) I
where
m is 1-3.
Particularly preferred herein are the thiols of formula:
RfCH2CH2SH
where
Rf is perfluoroalkyl of 6 to 12 carbon atoms. These Rf-thiols can
be prepared from RfCH2CH2I and thiourea in very high yield.
Component (C), an ionic non-fluorochemical water soluble surfactant
is chosen from the anionic, cationic or amphoteric surfactants as represented
in the tabulations contained in Rosen et al, Systematic Analysis of Surface-
Active A~ents, Wiley-Interscience, New York, (2nd edition, 1972), pp. 485-544,
which is incorporated herein by reference.
It iB particularly convenient to use amphoteric or anionic
- 29 -
10653Z7
fluorine-free surfactants because they are relatively insensitive to the
effects of fluoroaliphatic surfactant structure or to the ionic concentration
of the aqueous solution and furthermore, are available in a wide range of
relative solubilities, making easy the selection of appropriate materials.
Preferred ionic non-fluorochemical surfactants are chosen with
primary regard to their exhibiting an interfacial tension below 5 dynes/cm
at concentrations of .01-3% by weight. They should also exhibit high foam
expansions at their use concentration, be thermally stable at practically
useful application and storage temperatures, be acid and alkali resistant,
be readily biodegradable and non-toxic, especially to aquatic life, be readily
dispersible in water, be unaffected by hard water or sea water, be compatible
with anionic or cationic systems, form protective coatings on materials of
construction, be tolerant of pH, and be available commercially and inexpen-
sive.
In accordance with the classification scheme contained in Schwartz
et al, Surface Active Agents, Wiley-Interscience, N.Y., 1963, anionic and
cationic surfactants are described primarily according to the nature of the
solubilizing or hydrophilic group and secondarily according to the way in
which the hydrophilic and hydrophobic groups are ~oined, i.e. directly or
indirectly, and if indirectly according to the nature of the linkage.
Amphoteric surfactants are described as a distinct chemical cate-
gory containing both anionic and cationic groups and exhibiting special
behavior dependent on their isoelectric pH range, and their degree of charge
separation.
Typical anionic surfactants include carboxylic acids, sulfuric
esters, alkane sulfonic acids, alkylaromatic sulfonic acids, and compounds
with other anionic hydrophilic functions, e.g., phosphates and phosphonic
acids, thiosulfates, sulfinic acids, etc.
Preferred are carboxylic or sulfonic acids since they are
hydrolytically stable and generally available. Illustrative examples of
the anionic surfactants are
CllH230(C2H40)3 5S03Na
10653'~7
11 23 2 2 3
12 25 3
Disodium salt of alkyldiphenyl
ether disulfonate
Disodium salt of sulfosuc-
cinic acid half ester derived
alcohol 10-12 ethoxylated
Sodium Alpha olefin sulfonates
CllH23CONH(CH3)C2H4S03Na
CllH23coN(cH3)cH2co2Na
Typical cationic classes include amine salts, quaternary ammonium
compounds, other nitrogenous bases, and non-nitrogenous bases, e.g.
phosphonium sulfonium, sulfoxonium, also the special case of amine oxides
which may be considered cationic under acidic conditions.
Preferred are amine salts, quaternary ammonium compounds, and
other nitrogenous bases on the basis of stability and general availability.
Non-halide containing cationics are preferred from the standpoint of cor-
rosion. Illustrative examples of the cationic surfactants are
bis(2-hydroxyethyl)tallowamine oxide
dimethyl hydrogenated tallowamine oxide
isostearylimidazolinium ethosulfate
cocoylimidazolinium ethosulfate
lauroylimidazolinium ethosulfate
[ 12H250cH2lcHcH2T(cH2cH2oH2]cH3so4 t3
3 3
[ 11 23CONH(CH2)3N(CH3)3] CH3S04 ~
[ 17 35CONH(CH2)3N(CH3)2CH2CH20H] + N03 -
The amphoteric non-fluorochemical surfactants include compounds
which contain in the same molecule the follo~ing groups: amino and carboxy,
amino and sulfuric ester, amino and alkane sulfonic acid, amino and aromatic
sulfonic acid, miscellaneous combinations of basic and acidic groups, and the
special case of aminimides.
Preferred non-fluorochemical amphoterics are those which contain
- 31 -
106S3Z'7
amino and carboxy or sulfo groups, and the Pminimides.
The aminimide surfactants have been described in Chemical Reviews
Vol. 73, No. 3 (1973). Generally, they are the carboxaminimides of the
general formulae:
/ Rl R5
R(H) -C-N-N - R2 or R(H)n-C-N-N \ C~IR4-C - OH
R3 R2 R6
and sulfonylaminimides of the general formulae:
Rl R1 R5
R(H)nS02N-N - R2 or
R3 R2 R6
aminocyanoimides, aminonitroimides, or functionally substituted aminimides as
described in United States 3,499,032, United States 3,485,806 and British
1,181,218.
Of the above-mentioned aminimides, the carboxaminimides are most
preferred because of the combination of very desirable surface active prop-
erties listed below:
a) they are highly surface active and possess very low inter-
facial tensions at low concentrations and hence afford films of exceedingly
high-spreading coefficient;
b) they are amphoteric and thus compatible with all types of
fluorosurfactants - anionic, cationic, nonionic, or amphoteric;
c) they are thermally stable at practically useful application
0 and storage temperatures;
d) they are acid and aIkali stable;
e) they are biodegradable and non-toxic;
f) they are readily dispersible in water;
g) they are high-foaming and only moderately affected by water
hardness;
h) they are inexpensive and commprcially available.
Illustrative examples of the non-fluorochemical amphoteric
- 32 -
~0653'~7
surfactants are:
coco fatty betaine (C02 )
cocoylamidoethyl
hydroxyethyl carboxymethyl
glycine betaine
cocoylamidoammonium
sulfonic acid betaine
cetyl betain (C-type)
a sulfonic acid betaine derivatiYe
C~3
CllH23CONNCHOHCH3
CH3
CH
~ ~3
C13H27COl CH2CHHC 3
CH+3
Cl5H3lcoN~(cH3)2cH2cHoHcH3
C17H35CNN(CH3)2CH2CHHCH3
_+
_+
C15H31CONN(CH3)3
N ~ 2 ~ CH
ll I / 2 2 CH2C2
11 23
~CH2C02Na
A coco-derivative of the above
Coco Betaine
C12 14H25_29NH2CH2CH2
(triethanolammonium salt)
5~ \
CH2CH2C2Na
- 33 -
106S3Z7
A nonionic non-fluorochemical surfactant component (D) is incor-
porated in the aqueous fire compositions primarily as a stabili~er and sol-
ubilizer for the compositions, particularly uhen they are diluted uith hard
water or sea water. The nonionics are chosen primarily on the basis of their
hydrolytic and chemical stability, solubilization and emulsification char-
acteristics (e.g. measured by XLB-hydrophilic-lipophilic balance), cloud
point in high salt concentrations, toxicity, and biodegradation behavior.
Secondarily, they are chosen with regard to foam expansion, foam viscosity,
foam drainage, surface tension, interfacial tension and wetting character-
istics.
Typical classes of nonionic surfactants useful in this invention
include polyoxyethylene derivatives of alkylphenols, linear or branched
alcoholæ, fatty acids, mercaptans, alkylamines, alkylamides, acetylenic
glycols, phosphorus compounds, glucosides, fats and oils. Other nonionics
are amine oxides, phosphine oxides and nonionics derived from block polymers
containing polyoxyethylene and/or polyoxypropylene units.
Preferred are polyoxyethylene derivatives of alkylphenosl, linear
or branched alcohols, glucosides and block polymers of polyoxyethylene and
polyoxypropylene, the first two mentioned being most preferred.
Illustrative examples of the non-ionic non- n uorochemical
surfactants are
Octylphenol(EO)9 10
" (EO)16
" (EO)30
Nonylphenol (EO)g 10
(E)12 13
Lauryl ether (EO)23
Stearyl ether (EO)lo
Sorbitan nolaurate (EO)20
Dodecylmercaptan (EO)lo
Block copolymer of (EO)x(PO)4
CllH23cONtc2H~oH)2
~ 3~ ~
10653~7
C12H25N(CH3)20
~( CH2CH20 )xH
C12H25~ ~
(CH2CH20) H
x + y = 25
NOTE: EO and PO used above mean ethylene and propylene oxide repeating
unit, respectively.
Component (E) is a solvent which acts as an antifreeze, a foam
stabilizer or as a refractive index modifier so that proportioning systems
can be field calibrated. Actually, this i8 not a necessary component in the
composition of this invention since very effective AFFF concentrates can be
obtained in the absence of a solvent. In fact, this is one of the unexpected
and unusual features of this invention since prior art compositions as a rule
must employ a relatively high percentage of a solvent. However, even with
the compositions of this invention it is often advantageous to employ a sol-
vent especially if the AFFT concentrate will be stored in subfreezing tem-
peratures. Useful solvents are disclosed in United States patents
3,457,172; 3,422,011 and 3,579,446, and German patent 2,137,711.
Typical solvents are alcohols or ethers such as:
ethylene glycol monoalkyl ethers,
diethylene glycol monoalkyl ethers,
propylene glycol monoalkyl ethers,
dipropylene glycol monoalkyl ethers,
triethylene glycol monoalkyl ethers,
l-butoxyethoxy-2-propanol, glycerine, diethyl carbitol, hexylene
glycol, butanol, t-butanol, isobutanol, ethylene glycol and other
low molecular weight alcohols such as ethanol or isopropanol
wherein the alkyl groups contain 1-6 carbon atoms.
Preferred solvents are l-butoxyethoxy-2-propanol, diethyleneglycol
monobutyl ether, or hexylene glycol.
Still other components which may be present in the formulation are:
--Buffers whose nature is essentially non-restricted and which are exem-
- 35 -
10653Z7
plified by Sorensen's phosphate or McIlvaine's citrate buffers.
--Corrosion inhibitors whose nature is non-restricted so long as they are
compatible with the other formulation ingredients.
--Chelating agents whose nature is non-restricted, and which are exemplified
by polyaminopolycarboxylic acids, ethylenediaminetetraacetic acid, citric
acid, gluconic acid, tartaric acid, nitrilotriacetic acid, hydroxyethyl-
ethylenediaminetriacetic acid and salts thereof.
--High molecular weight foam stabilizers such as polyethyleneglycol,
hydroxypropyl cellulose, or polyvinylpyrrolidone.
The concentrates of this invention are effective fire fighting
compositions at any pH level, but generally such concentrates are ad~usted
to a pH of 6 to 9, and more preferably to a pH of 7 to ô.5, with a dilute
acid or alkali. For such purpose may be employed organic or mineral acids
such as acetic acid, oxalic acid, sulfuric acid, phosphoric acid and the
like or metal hydroxides or amines such as sodium or potassium hydroxides,
triethanolamine, tetramethylammonium hydroxide and the like.
As mentioned above, the compositions of this invention are con-
centrates which must be diluted with water before they are employed as fire
fighting agents. Although at the present time the most practical, and there-
fore preferred, concentrations of said composition in water are 3% and 6~because of the availability Or fire fighting equipment which can automatically
admix the concentrate with water in such proportions, there is no reason why
the concentrate could not be employed in lower concentrations of from 0.5%
to 3% or in higher concentrations of from 6% to 12%. It is simply a matter
of convenience, the nature of fire and the desired effectiveness in extin-
guishing the flames.
An aqueous AFFF concentrate composition which would be very useful
in a 6% proportioning system comprises
A) 1.0 to 3.5g by weight of amphoteric fluorinated surfactant,
B) 0.1 to 2.5% by weight of anionic fluorinated surfactant,
C) 0.1 to 4.0% by weight of ionic nonfluorochemical surfactant,
D) 0.1 to ô.0% by weight of a nonionic non-fluorochemical surfactant,
- 36 _
10653;~7
E) 0 to 20% by weight of solvent and water in the amount to make up the
balance of 100%.
The subject composition can be also readily dispersed from an
aerosol-type container by employing a conventional inert propellant such as
Freon* 11, 12, 22 or ~2' ~2 or air. Expansion volumes as high as 50 based
on the ratio of air to liquid are attainable.
The most important elements in this new AFFF system are the
amphoteric Rf-surfactants of component (A).
These amphoteric Rf-surfactants reduce surface tensions of the
aqueous solutions to about 20 dynes/cm ana act as solubilizers for the Type
B Rf-surfactants contributing to most of the excellent characteristics of the
novel AFFF agents of this invention. The anionic Rf-surfactants of component
(B) act as surface tension depressants for the amphoteric surfactant of com-
ponent (A) (synergistic Rf-surfactant mixtures) depressing the surface tension
to 15-16 dynes/cm and are usually present in a much lower concentration than
the Rf-surfactants of component (A). Rf-surfactants of component (B) further-
more increase the spreading speed of aqueous AFFF films on hydrocarbon fuels
and contribute significantly to the excellent resealing capacity of the novel
AFFF agent. The ionic or amphoteric hydrocarbon surfactants of component (C)
have a dual function. They act as interfacial tension depressants by reduc-
ing the interfacial tension of the aqueous Rf-surfactant solution containing
components (A) and (B) Rf-surfactants, from interfacial tensions as high as
10 dynes/cm to interfacial tensions as low as .1 dyne/cm. Furthermore, the
cosurfactantf of component (C) act as foaming agents and by varying the amount
and proportions of component (C) cosurfactants, it is possible to vary the
foam expansion of the novel AFFF agent. The nonionic hydrocarbon surfactants
of component (D) in the novel AFFF agent have also a multiple function by
acting as solubilizing agents for the Rf-surfactants of components (A) and
(B) having poor solubility characteristics. They furthermore act as stabiliz-
ing agents, especially of AFFF agent sea water premixes and also influence
the AFFF agent foam stability and foam drainage time as expalined later.
Furthermore they influence the viscosity of A~ agents which is very
*Trademark - 37 -
10~53Z7
critical especially in the case of 1% proportioning systems. Solvents of com-
ponent (E) are used similarly as solubilizing agents for Rf-surfactants, but
also act as foam stabilizers, to serve as refractive index modifiers for
field calibration of proportioning, to reduce the viscosity of highly con-
centrated AFFF agents, and as anti-freezes. Whereas commercial 6% propor-
tioning AFFF agents have high solvent contents of greater than 20%, this
invention teaches the preparation of comparable formulations with excellent
performance at solvent contents as low as 3%.
Some of the solvents present in the formulated AFFF agents are only
present because they are carried into the product from the ~f-surfactant
synthesis. Besides the contribution the ingredients so far listed may have
on the performance of the novel AFFF agent, it must also be mentioned that
these candidates were also selected because they have very low toxicity as
shown in the experimental part of this application. As mentioned before other
additives in the novel AFFF agent might be advantageous such as:
Corrosion inhibitors (for instance in the case where aqueous AFFF premixes are
stored for several years in uncoated aluminum cans).
Chelating agents (if premixes of AFFF aeents and very hard water are stored
for longer periods of time).
~uffer systems (if a certain pH level has to be maintained for a long period
of time).
Anti-freezes (if AFFF agents are to be stored and used at sub-freezing tem-
peratures).
Polymeric thickenin~ agents (if higher viscosities of AFFF agent -- water
premixes are desired because of certain proportioning system requirements),
and so on. Today's commercial AFFF agents are only capable of use on 6 and
3% proportioning systems. The composition of the instant AFFF agents and the
ranges of the amounts of the different active ingredients in these novel AFF
aeents will be expressed for 0.5 to 12% proportioning systems. If the con-
centration in a composition for 6% proportioning is doubled then such a con-
centrate can be used for a 3% proportioning system. Similarly if the con-
centration of such a 6% proportioning system is increased by a factor of 6
_ 38 _
10653Z7
then it can be used as a 1% proportioning system. As comparative data in
the experimental part will show it is possible to make such 1% proportioning
systems primarily:
A. Because of the higher efficiency of the novel Rf-surfactants
used and the smaller amounts therefore needed.
B. Because of the rather low amounts of solvents required in the
new AFFF agents to achieve foam expansion ratios as specified by the military.
In the examples, references are made to specifications used by the
induætry and primarily the military and to proprietary tests to evaluate the
efficiency of the claimed compositions. More specifically, the examples
refer to the following specifications:
Surface Tension and Interfacial Tension - ASTM D-1331-56
Freezing Point - ASTM D-1177-65
pH - ASTM D-1172
Sealability Test
Ob,~ective: To measure the ability of a fluorochemical AFFF formula-
tion (at the end use concentration) to form a film across, and seal a cyclo-
hexane surface.
Procedure: Ten mls of cyclohexane is pipetted into a 40 mm evap-
20 orating dish in the evaporometer cell. Helium flowing at 1000 cc per minuteflushes the cyclohexane vapors from the cell through a 3 cm IR gas cell
mounted on a PE 257 infrared spectrophotometer (a recording infrared spectro-
~hotometer with time drive capability). The IR absorbence of the gas stream
in the region of 2050 cm is continuously monitored as solutions of formula-
tions are infused onto the surface. Formulations are infused onto the cyclo-
hexane surface at a rate of 0.17 ml per minute using a syringe pump driven
lcc tuberculin syringe fitted with a 13 cm 22 gauge needle, whose needle is
~ust touching the cyclohexane surface.
Once the absorbence for 'tunsealed" cyclohexane is established, the
30 syringe pump is started. Time zero is when the very first drop of formula-
tion solution hits the surface. The time to 50% seal, percent seal at 30
seconds and 2 minutes are recorded. Time to 50~ seal relates well to film
39
10653'~7
speed (see below) percent seal in 30 seconds and 2 minutes relate well to
the efficiency and effectiveness of the film as a vapor barrier.
Film S~eed Test
ObJective: To determine the speed with which an AFFF film spreads
across a cyclohexane surface.
Procedure: Fill a 6 cm a~uminum dish one-half full with cyclo-
hexane. Fill a 50 ~1 syringe with a 6% solution of the test solution. In~ect
50 ~1 of the solution as rapidly and carefully as possible down the wall of
the dish such that the solution flows gently onto the cyclohexane surface.
Cover the dish with an inverted Petri dish. Start the timer at the end of
the inJection. Observe the film spreading across the surface and stop the
timer the moment the film completely covers the surface and record the time.
Match Test
Ob~ective: To determine roughly the sealing ability of an AFFF
fil~.
Procedure: Fill an aluminum weighing dish (58 x 15 mm) two-thirds full with
reagent cyclohexane. Carefully pour about 2 ml of test AFFF solution over
the surface. Strike a wooden match, and after the initial flare-up of the
match has subsided, immerse the flame quickly through the sealed surface and
then retract it from the dish. The flame will be snuffed out. Repeat with
additional matches until sustained ignition is achieved and note the number
of matches used.
Fire Tests
The most critical test of the subJect compositions is actual fire
tests. The detailed procedures for such tests on 2.60 sq.m., 4.647 sq.m. and
117.0 sq.m. fires are set forth in the United States Navy Specification
MIL,F-24385 and its Amendments.
Procedure: Premixes of the compositions of this invention are pre-
pared from 0.5 to 12% proportioning concentrates with tap or sea water, or
the AFFF agent is proportioned by means of an in-line proportioning system.
The test formulation in any event is applied at an appropriate use concentra-
tion.
~ 40
10653Z7
The efficacy of the compositions o~ the present invention to extin-
guish hydrocarbon fires was proven repeatedly and reproducibly on 2.60 sq. m.
gasoline fires as well as on 117.0 sq. m. fires conducted on a 12.19 m in
diameter circular pad. The tests were frequently conducted under severe
environmental conditions with wind speeds up to 16 km per hour and under
prevailing su~mer temperatures to 35C. The fire performance tests and sub-
sidiary tests -- (foamability, film formation, sealability), film speed, vis-
cosity, drainage time, spreading coefficient, and stability, all confirmed
that the compositions of this invention performed better than prior art AFFF
compositions.
The most important criteria in determining the effectiveness of a
fire fighting composition are:
1. Control Time - The time to brin8 the fire under control or
secure it aM er a fire fighting agent has been applied.
2. Extinguishing Time - The time from the initial application to
the point when the fire is completely extinguished.
3. Burn-Back Time - The time from the point when the flame has
been completely extinguished to the time when the hydrocarbon liquid reignites
when the surface i9 sub~ected to an open flame.
4. Summation of % Fire Extinguished - When 4.645 or 117.05 sq. m.
~ires are extinguished the total of the "percent of fire extinguished" value
are recorded at 10, 20, 30 and 40 second intervals. Present specification
for 4.645 sq. m. require the "Summation" to fires be 225 or greater, for
117.05 sq. m. fires 205 or greater.
2.60 sq. m. Fire Test
This test was conducted in a level circular pan 1.83 m in diameter -
(2.60 square meters), fabricated from 0.635 cm thick steel and having sides
12.70 cm high, resulting in a freeboard of approximately 6.35 cm during tests.
The pan was without leaks so as to contain gasoline on a substrate of water.
The water depth was held to a minimum, and used only to ensure complete cov-
erage of the pan with fuel. The nozæle used for applying agent had a flow
rate of 7.57 1 per minute at 7.03 kg/sq. cm pressure. The outlet was mod-
- 41 -
10653'~7
ified by a "wine tip" spreader having a 3.175 mm wide circu'ar arc orifice
4.76 cm long.
The premix solution in fresh water or sea water was at 21C - 5.5 C.
The extinguishing agent consisted of a 6-percent proportioning concentrate
or its equivalent in fresh water or sea water and the fuel charge was 37.85
1 of gasoline. The complete fuel charge was dumped into the diked area within
a 60-second time period and the fuel was ignited within 60 seconds after com-
pletion of fheling and permitted to burn freely for 15 seconds before the
application of the extinguishing agent. The fire was extinguished as rapidly
as possible by maintaining the nozzle 1.07 to 1.22 m above the eround and
angled upward at a distance that permitted the closest edge of the foam pat-
tern to fall on the nearest edge of the fire. When the fire was extinguished,
the time-for-extinction was recorded continuing distribution of the agent
over the test area until exactly 11.36 1 of premix has been applied (90-
second application time).
The burnback test was started with 30 second after the 90-second
solution ~pplication. A weighted 30.48 cm diameter pan having 5.08 cm side
walls and charged with o.946 1 of gasoline was placed in the center of the
area. The fuel in the pan was ignited ~ust prior to placement. Burnback time
commenced at the time of this placement and terminated when 25 percent of the
fuel area (0.65 sq. meter), originally covered with foam was aflame. After
the large test pan area sustained burning, the small pan was removed.
117.0 sa. m. Fire Test
This test was conducted in a level circular area (117.0 sq. m.).
The water depth was the minimum required to ensure complete coverage of the
diked area with fuel. The nozzle used for applying the agent was designed to
discharge 189.27 1 per minute at 7.07 kg/sq.cm.
The solution in fresh water or sea water was at 20 C - 5.50C and
contPined 6.o - 0.1 % of the composition of this invention. The fuel was
1135.6 1 of gasoline. No tests were conducted with wind speeds in excess of
16 km per hour. The complete fuel charge was dumped into the diked area as
rapidly as possible. Before fueling for any test run, all extinguishing
- 42 -
~0653'~7
agent from the previous test run was remo~ed from the diked area.
The fuel was ignited within 2 minutes after completion of fueling,
and was permitted to burn freely for 15 seconds before the application of the
extinguishing agent.
The fire was extinguished as rapidly as possible by maintaining the
nozzle 1.07 to 1.22 m above the ground and angled upward at a distance that
permitted the closest edge of the foam pattern to fall on the nearest edge
of the fire.
At least 85 percent of the fire was to be extinguished within 30
seconds, and the "percent of fire extinguished" values were recorded.
Example 1
N~3-(dimethylamino)propyl]-2 and 3-(1.1~2.2-
tetrahydroperfluorodecylthio)succinamic acid
C8F17CH2CH2SCHCOo ~)
CH2coNH(cH2)3NH(cH3)2 and
C8Fl7cH2cH2scHcoNH(cH2)3NH(cH3)2
CH2COO ~)
Maleic anhydride (10.0 g; 0.102 mole) and a mixture of ethyleneglycol dimethyl ether (100 g) and N,N-dimethyl formamide (60 g) were placed
in a stirred reaction flask kept under nitrogen atmosphere and cooled to 10C
in an ice bath. 3-dimethylaminopropylamine (10.4 g; 0.102 mole) was added
drop-wise during one-half hour at a reaction temperature of 10-15 C. The
resulting white suspension was stirred at room temperature for 1 hour.
A small amount of this product was dried, washed with heptane and
dried in vacuo at 30C for 12 hours. Infrared analysis and NMR signals were
characteristic for a compound of structure:
/coo ~
HC
HC \
CONH-(CH2 )3N(CH3)2
N-(3-dimethylaminopropyl) maleic acid amide.
~ 43 ~
10653Z7
1,1,2,2-tetrahydroperfluorodecyl mercaptan (4~.0 g; 0.102 mole) was added all
at once. l`he resulting mixture was stirred for 64 hours at roo~ temperature.
The thick suspension was filtered and the solids washed with acetone then
dried at room temperature under vacuum (0.1 mm Hg) for lô hours. The product
was obtained as a white powder weighing 61.2 gms (yield = 88.2%) having a
m.p. of 123-128 with slow decomposition (gas evolution) above the melt. The
infrared spectrum was consistent with the structure in particular the amide
band at 1650 cm in the solid phase and at 1660 cm 1 in dilute chloroform
solution and the carboxylate asymmetrical and symmetrical stretching bands at
1550 cm and 1320 to 1390 cm 1 respectively. An ~MR spectrum was consistent
with the structure and showed the ~ollowing signals:
2-68 ppm ~-CH3i 1.8-2.1 NCH2CH2CH2N
CH3
The surface tension (~ ) of the aqueous solution of the above named
compound is 19.8 dynes/cm. The surface tension in this and the following
examples was measured with a Du Nouy tensiometer at 0.1 % concentration in
water at 25C.
Example 2
N-~3-(dimethvlamino)propyl~ -? and 3-(1.1~2~2-
tetrahydroperfluoroalkylthio)succinamic acid
RfCH2CH2SCHC ~
CH2CONH(CH2)3NH(CH3)2
and its isomer
Maleic anhydride (100 g; 1.02 le) and N-methylpyrrolidone (400 g)
were stirred in a reaction flask under an inert atmosphere and cooled to 0 C
in an ice-salt mixture. 3-Dimethylaminopropylamine (106 g; 1.04 mole) dis-
solved in N-methylpyrrolidone (100 g) was added drop-wise during 40 minutes
at 0-10 C. The dark tan suspension was stirred at room temperature for 20
minutes when methanol (800 g) was added and the resulting mobile suspension
was heated to 45C. 1,1,2,2-Tetrahydroperfluoroalkyl mercaptan ~483 gi 0-94
mole) (a mixture of compounds having varying alkyl groups as follows: C6-25
-44 -
1065327
C8-50%; and Clo-25%) was added during 10 minutes at 45-50C to give an amber
solution which was stirred at 45C for 3 hours. The completenessof reaction
was checked by the disappearance of perfluoroalkylethyl mercaptan to trace
amounts of the reaction mixture, as detected by gas chromatography. Identity
of the product was confirmed by infrared absorption for the a~ide function at
1655 cm 1 and the carboxylate ran at 1560 cm 1 and 1325-1400 cm 1. Gas
chromatography showed three perfluoroalkyl acid areas, two solvent areas and
trace areas due to the mercaptans. Proton NMR signals obtained were essen-
tially identical to those for Example 1. The compound melted at 95 to 115 C.
~he surface tension of the aqueous solution of said compound was 17.7 dynes/
cm.
Following the procedure described abo~e, compounds analogous to
Example 2 were prepared from maleic anhydride and the following indicated
starting materials;
10653Z7
_
C~ ~o ~ ~ ~ o~
m
~ 2 ~ 2 ,,
~o
N N
N N ~ ~ ~ W :1; V
I ~i CU I
I CU ~ t!~ I
O ~N I N C.)
C.) N Z_ ~C N
~N
O N ~U N N N
~1 C~
~0 ~ ~0
--46
10653Z7
Exam~le 8
N-met~yl-N-(2'-N',N'-dimethylaminoethyl)-2 and
3-~1 1,2,2-tetrahydroperfluoroalkylthio)suc-
cinamic acid
RfCH2CH2S-CHC ~ ~ / CH3
CH2C07-CH2CH2NH \ and isomer
CH3 CH3
Rf is a mixture of C6F13 (25%), C8F17 (50%) and CloF21 (25%)
Powdered maleic anhydride (0.033 moles, 3.24 g) was added in por-
tions to a cooled solution of (N,N',N'-trimethyl)-ethylene-1,2-diamine
(0.033 moles, 3.47 g) in 6.7 g water. The reaction was carried out under
nitrogen and maintained at 10-20C with an ice bath. After the addition
was complete the bath was removed and the reaction mixture was stirred at
room temperature for 12 hours.
A small amount of the solution was dried in vacuo at 30 C for 12
hours. A dry, white powder was obtained whose NMR signals were charac-
teristic for a compound of structure:
H3C CH3
\~/
N CH2C
~H
CH3No acidic hydrogen could be titrated.
2-methyl-2,4-pentane diol (20.13 g) was added to the light yellow
solution followed by perfluoroalkyl ethyl mercaptan (0.3135 moles, 14.65 g).
The resulting white suspension was heated to 90 C with stirring until the
completion of the reaction (6.5 hours). The clear light yellow solution was
cooled to room temperature and diluted to 30% solids with water (23 g). The
turbid solution was clarified by filtration (5~ porosity asbestos pad) to
yield 66.5 g (93.4%) of a clear light yellow solution. Infrared analysis
was consistent with the structure. The surface tension ( ~s) of the aqueous
- 47 -
iO653'X7
solution of the above compound was 18.3 dynes/cm.
Example 9
Following the above procedure, the compound N-ethyl-~-(2'-N'N-
dimethylaminoethyl)-2 and 3 -(1,1~2,2-tetrahydroperfluoroalkylthio)succinamic
acid was prepared from maleic anhydride, RfC2H4S~ and N,~-dimethyl-N'-ethyl-
ethylene-1,2-diamine. The surface tension of this co~pound was 20.2 dynes/cm.
Example 10
N-(2-dimeth~laminoethvl)-2 and 3-(1~1~2~2-tetra-
hydroperfluoroalkylthio)succinamic acid
RfCH2CH2S-CHCOO ~)
¦ ~ / CH3
2C0 ~ CH2CH2 N H \ and isomer
H CH3
Powdered maleic anhydride (0.033 moles, 3.24 g) was added in por-
tions to a cooled solution of (N,N-dimethyl)-ethylene-1,2-diamine (0.033
moles, 2.90 g) in 6.7 g water. The reaction was carried out under nitrogen
and maintained at 10-20C with an ice bath. After the addition was complete
the bath was removed and the reaction mixture was stirred at room temperature
overnight, 2-methyl-2,4-pentane diol (20.13 g) was added to the light yellow
solution followed by perfluoroalkyl ethyl mercaptan (0.3135 moles, 14.65 g).
The resulting white suspension was heated with stirring at 30C to completion
(6.5 hours). The light yellow solution was cooled to room temperature and
diluted to 30% solids with water. It was clarified by filtration through a
5 ~ porosity asbestos pad to yield 66.5 g (93.4%) of a clear light yellow
solution. The surface tension of the aqueous solution of the above compound
was 22.0 dynes/cm.
Following the procedure described above, compounds analogous to
Example 10 were prepared from maleic anhydride and the starting materials as
shown below:
- 48 ~
106S3Z7
. ~1 ' . .
U~ . , . .. ,
. .
,, ~ .,
~ ~ ~ .
.: . ~
~ C~
E~ ~ - t~
., ~ :r:
~, m~ ~ "~ . .
~ ~> X U~
o
æ ~
U
'
.
_~ ~ W
o V~ U~
r~ ~ er
.c
. C,)~ ~
~ ~ o~ , .,
o
Z . -
X ~ _~
~
~9 -
,
10653'~7
~ .
oo
a) ,~
~1 ~ ~1
" ' . ' . ,
U~
X
N`. ~`J
U . ~ ~ U
o ~ m
'C.~ ~ U' :Z
V 1 ~ Z
-
O u~
.C 3~ . :C
~ ~ ~ c) ~
Z r
-~0--
~0653~7
.
.
~ . -'
m ~ o ~r ~ . .
F~ N ~D t` . ~ r~
~ ~`1 ~I N ~1 ~1
~ . ',
,
~ ,
O . ,~, Z
O I ~)
t~~ Z ~ ~ :~
m ~3 Z~ ~
m N -
~r ~ ~ ~ ~r
~ r m ~ ~
o <~ .
.
~` t` I~ ~ ~
I ~ I ,~ I
h
00 00, ~D ~D
. ~ O
.q
Z t` CO o~ - o ,~
~1 ,1 _I
,. ~
.~ . ' ' ,'''''.
- 51 - -
.
10653Z7
Example 22
2 and 3~ 2~2-tetrah~droperfluorodecylthio)
succinic acid-mono-[2-(N,N-dimethyl)aminoethyl~
ester
C8F17CH2cH2scHcoo ~ / CH3
CH2COOCH2CH2NH \ and isomer
CH3
A solution of maleic anhydride (o.o408 moles, 4.00 g) in acetone
(15 g) was added to N,N-dimethyl aminoethanol (o.o408 moles, 3.64 g) in
acetone (10 g) at 10 C. The product precipitated as an acetone insoluble
resin. After 30 minutes methanol (20 g) was added and a dispersion was
formed. 1,1,2,2-tetrahydroperfluorodecyl mercaptan (.o408 moles, 19.6 g)
was added and as the reaction proceeded, a clear solution was formed.
The reaction was allowed to stand at room temperature for 24 hours. VPC
and TLC showed no unreacted mercaptan. The yellow solution was dried
under vacuum to a light yellow wax. The Yield was 26.5 g (98.5%).
The surface tension ( ~s) of the aqueous solution of the above
named compound is 16.3 dynes/cm.
Following the procedure described above, compounds analogous to
Example 22 were prepared from maleic anhydride and the starting materials
shown below:
-52 _
10653Z7
a) o ~ ~ ~ ~ N
r~ 1 ~', ~ N N
U~
.
}~'
. , ' X
~ ~ ,
8 o N ~ T ~ ~ ~
O ~ ~ N
z _ N ~DN b~N X ~ N
' U ~ U ~
., , , ~, ~ .
- 1 ¦ U ~ U ~N ~N N
p; C~ U tA~ ~ C) U
G)
~;
. ' ''
...... . . ., ~ ,_, , . _ _.,,, .. ,.. .. _ . ._ .. . . . .
10653Z7
Example 29
2 and 3-(1,1,2~2-tetrahydro~erfluorodecylthio)
succinic acid mono-(2'-quinolino ethyl)
ester
CôFl7cH2cH2s-lcHcoo ~ and isomer
CH2COOCH2CH2~
A solution of maleic anhydride (0.0255 moles,
2.5 g) in dichloromethane (10 g) was added dropwise
to a stirred solution of 2-(2-hydroxyethyl)-quinoline
(0.0255 moles, 4.2 g) in dichloromethane (20 g). The
mixture was cooled to 0C and kept at -10 C during
the addition. A Mer the addition was completed the
dry ice/acetone bath was removed and the reaction mix-
ture was allowed to warm up slowly to 20 C. Then 1,1,
2,2-tetrahydroperfluorodecyl mercaptan (0.0255 moles,
12.24 g) were added. The brown solution was allowed
to stand overnight at room temperature and then heated
to 26 C for 2 hours. TLC and VPC showed no unreacted
mercaptan. The solution was dried under vacuum to
yield 18.2 g of a light brown powder (94.8~).
The surface tension t ~ s) of the aqueous
solut~on of the above named compound is 22 dynes/cm.
_ ~4 -
10653Z7
Example 30
N~N'-bis[(n-propyl-3)-2 and 3-(1~1~2~2-tetrahydro-
perfluorooctylthio)succinamic monoamido3piPerazine
C6F13CH2CH2s- lcH-coo ~ OOC-7H-S-CH2CH2C6Fl3
CH2CNHCH2CH2CH2N ~ NHCH2CH2CH2 11 2
and isomer
1,4-bis(3-aminopropyl)piperazine (0.0255
moles, 5.1 g) in 10 g acetone was added dropwise to
a dry ice/isopropanol cooled solution of maleic
anhydride (0.0510 ~oles, 5.0 g) at -10 to 0C. A
white precipitate came out immediately and the
reaction mixture was stirred for one hour at 20 C.
1,1,2,2-tetrahydroperfluorooctyl mercaptan
(0.0510 moles, 19.27 g) was added and the reaction
was stirred for 3 days at room temperature until
TLC showed no traces of unreacted mercaptan. The
amber solution was dried under high vacuum to 29.1
of yellow powder (99% yield).
Infrared spectrum was consistent for the
structure.
The surface tension ( ~s) of the aqueous
solution of the above named compound is 22 dynes/cm.
~ 55 -
10653Z'7
Example 31
N[3-(dimethylamino)propyl]-2 and 3-(heptafluoro-
isopropoxy-1,1~2~2-tetrahydroperfluoroalkylthio)
succinamic acid
C~
~ (CF2)ncH2cH2s-cH-coo ~ ~ / CH3
CF3 C 2 HCH2CH2CH2NH \
CH3
and isomer
Maleic anhydride (0.0255 moles, 2.5 g) was
dissolved in 10 g acetone. 3-dimethylamino propyl~mine
(0.0255 moles, 2.61 g) in 5 g acetone was added dropwise
so that the reaction temperature was maintained at 5-10C.
As the reaction proceeded, an acetone insoluble resin
was formed and after the amine addition was completed
10 g methanol was added to form a homogeneous mixture
Heptafluoroisopropoxy-1,1,2,2-tetrahydro-
perfluoroalkyl mercaptan (0.0255 moles, 14.60 g) was
added and the reaction mixture was stirred for 2 days
until TLC showed no traces of the mercaptan. The pale
yellow solution was dried under vacuum to give 18.9 g
of white powder (95.9% yield).
Infrared analysis was consistent for the above
structure.
:10653Z'7
Example 32
N-[3-(dimethylamino)propyll-2 and 3-(1~1~2~2~
tetrahydroperfluorooctylthio) methylsuccinamic
acid
C6F13CH2CH2S-CH2
IH_COO ~
¦ ~ / CH3
2 HCH2 H2cH2NH \ and isomer
CH3
3-dimethylamino-propylamine (0.25 moles,
2.55 g) in 5 g acetone was added to a cooled solution
of itaconic anhydride (.025 moles, 2.80 g) in 10 g
acetone at 5-10C. There was an immediate exothermic
reaction and the light brown product precipitated out
slowly. 10 g methanol was added to dissolve the product
and the reaction mixture was stirred for one hour.
1,1,2,2-tetrahydroper n uorooctyl mercaptan
(.025 les, 9.45 g) was added and the reaction was
stirred for 2 d~ys at room temperature. TLC showed no
unreacted mercaptan. ~he clear amber solution was dried
under vacuum to give 14.0 g of a yellow wax (94.6% yield).
Infrared analysis was consistent with the above
structure.
10653'~7
Example 33
This example shows the preparation of
sulfonates by quaternization with propane sultone.
41.7 e (0.061 moles) of the surfactant
prepared in Example 1, was dissolved in an equal
amount of acetone and 7.45 g (0.061 moles) of propane
sultone was added, the reaction mixture was stirred
at 50C for 8 hours; the IR spectrum showed a strong
new band at 1035 cm 1, indicating formation of the
sulfonate; a C=0 band at 1660 cm as well as bands
at 1780 and 1710 cm 1, indicating that some imide had
been formed. No carboxylate and no dimethylamino
group was visible in thè IR spectrum which is generally
consistent with the structure shown below. The product
was a waxy solid which formed a strongly foaming aqueous
solution.
H
8 17 H2C 2 S IC COOX ~ 3
CH2-CON-CH2CH2CH2- _CH2CH2CH2S3
H ¦~
CH3
and its isomer.
Elemental analysis: C N S F
Calculated: 33.6 3.4 7.6 39.6
Found: 33.1 3.58.0 38.7
The surface tensio~ s) of the aqueous solu-
tion of the above named compound is 21.5 dynes/cm.
10653'~
On heating to 120 C for 30 minutes, itsIR spectrum changed. The band at 1660 cm 1 dis-
appeared completely and the two imide bands at
1780 and 1720 cm grew very strong, no carboxylate
and no dimethylamino absorption were present. This
IR spectrum was consistent with the structure:
8 17 2 2 CH C ~ ~ H3
l ~-cH2cH2cH2-l CH2CH2CH2 3
CH2-C CH3
The surface tension ( ~s) of the &queous
solution of the above named compound is 22.5
dynes/cm.
10653'~7
Example 34
Example 33 was repeated with the Rf-sub-
stituted succinamic acid of Example 16. The sulfonate
(A) for~ed easily and was a waxy, brown solid. On
heating imidization occurred to the compound of structure
(B)
COO~
C8Fl7cH2cH2-s-cH
H2C
2 ~ CH2CH2CH2S3 (A)
VheQt
~P
C8Fl7cH2cH2-s-cH ~
I ~ - CH2 ~ 2 H2 H2 3 (B)
H2C ~
The surface tension ( ~s) of the aqueous solu-
tion of the above named compound is 19.1 dynes/cm.
IR analysis of (A) and (B) were consistent
with the given structures.
Elemental analysis of (B)
C ~ S F
Calculated: 33.4 3.4 7.7 38.8
Found: 34.6 3.3 8.1 37.2
-6~ _
10653Z7
Example 35
This example shows the formation of Rf-sub-
stituted succinimide from the corresponding succinamic
acid.
IR analysis of the compound made in Example 1
revealed a strong carboxylate band at 1600 cm and a
strong C=0 band at 1660 cm consistent wlth structures:
C8F17-CH2CH2-s- I_COO ~3
CH2-co-l-cH2cH2cH2l(c~3)2 ~A)
H H
C Fl7-cH2cH2-s-lc-co~H-cH2cH2cH2~(c 3)2 (A')
CH2-COO
When thiæ material was heated to 120C for
20 minutes, it foamed slightly; it became insoluble
in water, but dissolved in acidic aqueous medium. Its
IR analysis showed two strong bands at 1780 and 1710 cm
characteristic for the cyclic imide with the bands at
1600 and 1660 cm reduced to weak shouldersj also
present was a strong absorption at 2770 and 2820 cm 1
characteristic for the dimethyl amino group. The spectrum
was consistent with the structure:
H
C8F17-CH2CH2-S-C C\ CH3
IH C ~ C 2CH2CH2 ~ ~ CH3 (B)
_ 61 -
~0653Z7
N-(~',N'-dimethyl-3-amino propyl)-2-(1,1,2,2-tetra-
hydro heptadecylfluorothiodecyl) succinimide.
Elemental Analysis for (B):
C N S F
Calculated: 33.4 4.1 4.7 47.5
Found: 34.2 4.0 5.3 46.4
The following examples describe the preparation
of additional quaternized derivatives.
Exam~le 36
2.04 g (0.003 mole) of [2 and 3-(1,1,2,2-tetra-
hydroperfluorodecyl thio)]-~,N-dimethyl(3-aminopropyl)
succinamic acid (of Example 1) were dissolved in 5cc
35% aqueous HCl. The clear solution was evaporated and
the residue dried in vacuo (0.1 mm Hg) at 80C for 12
hours, to yield 2.1 g of a white powder, having the
structure:
8 17 2 2 CIH COOH
CH2-CO~H-CH2CH2CH2~(CH3)2H Cl
and isomer
The surface tension ( ~s) of the aqueous
solution of the above named compound is 18.8 dynes/cm.
- 62 -
106S327
Example 37
2.04 g (0.003 mole) of 2 and 3-(1,1,2,2-
tetrahydroperfluorodecylthio)-N,N-dimethyl amino-
propyl succinamic acid melting at 123-128C was
sealed in an ampoule with 0.43 g (O.OG3 mole) methyl
iodide in 10 g isopropanol and heated for 3 hours.
The pale pink suspension was filtered and dried to
yield 1.6 g of white powder melting at 205-250C
having the structure
C8F17CH2CH2S-CH _ C ~ ~(CH ~ I
¦ NCH2CH2CH2N 3 3
CH2-C ~
The surface tension ~ ~s) of the aqueous
solution of the above named compound is 24.9 dynes/cm.
Exam~le 38
2.04 g (0.003 mole) of 2 and 3-(1,1,2,2-tetra-
hydroperfluorodecylthio)-N,N-dimethyl(3-aminopropyl)
succinamic acid was refluxed with 0.38 g (0.003 mole)
benzyl chloride in 10 g ~hanol until basic tertiary
amine was no longer detected. The æolution was evaporated
to yield 2.17 g of an off-white semi-solid having the
structure
~0
C8Fl7cH
¦ NCH2CH2CH2N(CH3)2CH2 ~ Cl
CH2-C
\\o
- 63 -
iO653Z7
The surface tension ( ~s) of the aqueous
solution of the above named compound is 20.8 dynes/cm.
Example 39
2.04 g (0.003 mole) of [2 and 3-(1,1,2,2-
tetrahydroperfluorodecylthio)]-N,N-dimethyl(3-amino-
propyl)succinamic acid was stirred with 0.28 g (0.003
mole) chloroacetic acid in 30 g water overnight. No
free tertiary amine was detectable. 20 g methanol
was added to break the foam and the clear solution
was evaporated at 60 C and vacuum to give 2.1 g of
off-white wax having the structure.
C8F17-CH2CH2Scx-c~ ~3
¦ CH2CH2CH2N(CH3)2CH2C00
CH2-C~
The surface ter,sion ( ~s) of the aqueous
solution of the above named compound is 17.4 dynes/cm.
- 6~ _
10653'~7
Exam~le 40
2.04 g (0.003 mole) of [2 and 3-1,1,2,2-
tetrahydroperfluorodecylthio]-N,N-dimethyl(3-amino
propyl)succinamic acid was dissolved in 30 ml ether.
A solution of 0.22 g (0.0031 mole) ~-propiolactone
in 5 ml ether was added dropwise over 5 minutes at
15C. The mixture was stirred for 2 hours at 30C
and the ether was removed in a rotary evaporator.
Yield: 2.2 g of a product having the structure:
8 17 2 2 C OH
H2 CONHCH2CH2CH2N(CH3)2CH2-CH2coo
and isomer
The surface tension ( ~s) of the aqueous
solution of the above named compound is 22.6 dynes/cm.
- 65 -
10653'~7
C~J N CO
l N CC
~ ) Xtr)
+~ +~
_ ~
V o ~ V
V O ~ V C~
I C~l C~l I C~ I CUI CU CU ~ -I
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,, ~ _ _ _
o ~ u~ rJ ~ o o '
h ~N N C~J ~!J ~ ~ æ 0
0 ~ 3 Vq,~
r; ~ V ~ ~ a
~-~1 0 ~
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~1 I ~ oU~
o ~ h
,1 ~o ~ o o 0 o o o ~ ,1 ~-
~ ~ ~1 a ~ o s~a h rl F~
0 a ~ ~ 3 ~ ~ h
E~ eh ~ h ~3 0~ h S 0 P~ r ~ r
u~ $ ~ A ~ ~ ~ to a
h h ~ ~.~o o~
^ e, - ~d ~1 1 '~d ~ - ~d ,1 u~ .,/ ,~ O
~:1 ~ ~ h ~ o
h ~ ~ ~ æ ~ z ~
z ~ 3 Z N ~ 3
`J cû a
C) ~ ~0 ~ æ ~ .# Xt,o
c~ æ ^ c~
h ~ ~ ~ d h
O I ~ ~ ~ ~ ~~ ~--` co ~d ,~ O
) _I U 0 0 ~ 0 00 rl ~
~ O
Z--~ Z ~ ~ ~ ~ Z
0 ~ ~I N tr~ J
s $ ~: ¢ ¢ ~c
~06S3'~7
_~ ^ ^ N
N gC~I ~N
lôcu loCU oC~l loCJ
~ _ -- O
~ V
O O O
i
S 9 ~ 9 ~ 9 1~ 3
9~ ~ ~
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--N ~: --N a _ N a _ N a
N ~ rl u ~ ~ 1 U
U ~ ^ ~ ~ ~ U ~ ~ C~
~ æ~ ~
~J ~ U~ ~ ~ ct:~
¢ c~
--67 -
10653A~7
Table 2
Anionic Fluorinated Surfactants* used in Examples 41 to 117
_. . _ . ... _
.Anionic . Formula - Actives -lOO~h or
Rf-Surfactant Name as ~ioted
.
Bl pel^fluoroalkanoic acid RfCO2H
B2 potassium perfluoroalkanoate 25% RfCO2K - 25% in lO hexylene
glycol -l5% t-butyl alcGh~cl
-~ ~later
B3 2 ~-dihydroper~luoroalkanoic acid RfCH2C02H
B4 sodium l l 2 2-tetrahydroperflu- RfCH2CH2S (C~2)3s03~a
oroalkylthio propanesulfonate
. R~ = C6 C8 C10
B5 perfluoro-
heptanoic acid75 25 Q C6Fl3C02H
B6 perfluoronon- .
anoic acid 4 87 9 C8FI7C02H
B7 perfluoro-
undecanoic acid 0 11.5 88.5 CloF2lCO2H
B8 potassium perfluoroheptanoate C6Fl3CO2K - 25% as in B2
_ _ _
~here Rf is typically a mixture of C6Fl3 (32%) C~Fl7 (~2~) and
CloF2l (6%) and traces of other homologs
-6 Y-
~o653'<:7
Table 3
Ionic (and Amphoteric) Surfactants used in Examples 41 to 117
. _
Type A-Anionic
Ionic C-Cationic
Surfactant AM-Amphoteric Name - % Actives as Noted or ~ 100%
Cl AM trimethylamine laurimide
C2 AM partial sodium salt of N-lauryl ~-
iminodipropionic acid (30%)
C3 AM N-lauryl, myristyl ~-aminopropionic
acid (50%)
C4 C cocoimidazolinium ethosulfate
C5 AM dimethyl(2-hydroxypropyl)amine
laurimide
C6 AM dimethyl(2-hydroxypropyl)amine
myristimide
C7 AM dimethyl(2-hydroxypropyl)amine
palmitimide
C8 AM trimethylamine myristimide
C9 AM acylamidoammonium sulfonic acid
betaine (50%)
C10 AM dicarboxylic lauric derivative-
imidazolinium amphoteric (38~)
Cll A sodium salt of ethoxylated lauryl
alcohol sulfate (27~)
C12 AM disodium salt of N-lauryl ~-
iminodipropionic acid
- 6g -
10653Z7
,ab1~ ~!
Nonionic Sur~actants used in Examp~es 41 to 117
Nonionic , Name
Surfactant X Actives as Noted or -100~ . -
~_
Dl octylphenoxypolyethoxyethano1 (12) 99~ -
D2 polyoxyethylene (23) lauryl ether
D3 octylphenoxypolyethoxyethanol (16) -70X
D4 octylphenoxypolyethoxyethanol (10) -99%
D5 octylphenoxvpo1yethoxyethanol (30) -70
D6 nonylphenoxypolyethoxyethanol (20)
D7 - nonylphenoxypolyethoxyethanol (30) -70X
D8 branched alcohol ethoxylate (15)
Numbers in brackets indicate ethylene oxide repeating units.
Table 5
Solvents used in Examples 41 to 117
Solvent Name
... _ . . .. . _ _ .
El l-butoxyethoxy-2-propanol
E2 1-butoxy-2-propanol/2-methyl-2,4-pentanediol 2/3 ratio
E3 diethylene glycol monobutyl ether
E4 2-methy1-2,4-pentanediol -.
E5 . tetrahydrothiophene-l,l-dioxide
E6 ethylene glycol
.. .
106S3Z7
Exam~les 41 to 44
AFFF agents having a composition as shown in Table 6
have identical compositions except that the Rf-group in the ampho-
teric Rf-surfactant varies from a pureperfluorohexyl to a pure
perfluorooctyl to a pure perfluorodecyl group, and to a mixture
Or perfluorohexyl, perfluorooctyl and perfluorodecyl in a ratio
of approximately 1:2:1.
As the surface tension data in Table 6 show, the lowest
values are obtained with the pure C8 isomer followed by the
amphoteric Rf-surfactant with mixed Rf-groups. On the other
hand, lowest interfacial tension values are obtained with the
C6 isomer and the Rf-isomer mixture. As a result the hiehest
spreading coefficient of 6.5 dynes/cm is obtained with the
Rf-mixture. Rf-mixture amphoteric fluorinated surfactants of
mype A with mixed Rf-groups are, of course, from an economical
standpoint, most desirable.
The pH-values of the compositions in these and the
following examples are generally in the range of 7 to 8.5,
unless otherwise mentioned.
10653'~7
Table 6
~ffect of Amphoteric Rf-Surfactant (Component A) and its Homolog Content
Example ~os. 41 to 44
Amphoteric Rf-Surfactant Solution Various: (as stated)
Anionic Rf-Surfactant . . . . . . . . Bl: 0.29 %
Amphoteric Cosurfactant . . . . . . . C2: 8.33 % (30 % solids)
~ther Cosurfactant . . . . . . . . . C4: 0.83 %
~onionic Cosurfactant . . . . . . . . D2: 2.08 %
Solvent . . . . . . . . . . . . . . . El: 5.00 %
Water . . . . . . . . . . . . . . . . . . Balance
Example ~o. 41 42 43 44
. .
Rf-surfactant A6, 30 % as is 4.93
Rf-surfactant A7, 30 % as is 4.93
Rf-surfactant A8, 100 % as is 1.48
Rf-surfactant Al, 30 % as is 4.93
Surface tension* dynes/cm 17.7 16.9 18.0 17.2
Interfacial tension* dynes/cm 9 1.7 1.7 0.9
Spreading coefficient* dynes/cm 6.o 6.0 4 9 6.5
* 3 percent dilution in distilled water; interfacial tension
against cyclohexane
10653A~7
Examples ~5 to 50
AFFF agent compositions as listed in Table 7 have
identical compositions with the exception of the anionic
fluorinated surfactants of Type B, which vary from a perfluoro-
hexyl to a per M uorooctyl, to a per n uorodecyl group and mixtures
of Rf-groups as defined in Table 2. Lowest surface tension data
are obtained with per M uorooctyl and a. mixed perfluoroalkyl
group-containing nonionic surfactants of Type B. Similarly,
these preferred compositions show the fastest film speed.
Most important of the results shown in Table 7 is the
fact that an AFFF agent not containing any of the anionic
fluorinated surfactant of Type B has much higher surface tensions;
therefore, a lower spreading coefficient, ro film resealing
properties and, in addition, a very slow film speed.
10~53Z7
Examples 51 to ~7
Surface property measurements shown in Table 8 show
that aqueous solutions of amphoteric Rf-surfactants of Type A,
have low surface tensions, but high interfacial tensions
(measured against hydrocarbons such as cyclohexane), and such
aqueous solutions have, therefore, negative spreading co-
efficients. By the addition Or amphoteric cosurfactants
of Type C to aqueous solutions of amphoteric Rf-surfactants
of Type A it is posæible to lower the interfacial tension
properties and achieve these very high spreading coefficients.
Amphoteric cosurfactants of Type C are therefore referred to
as interfacial tension depressants, even though they con-
tribute to other properties of AFFF agents, such as foaming,
stability, etc. Examples 51 to 56 show how the interfacial
tension of a 0.1 percent aqueous solution of the amphoteric
Rf-surfactant A5 is reduced by the addition of the preferred
fatty aminimide surfactants of Type C, as listed in Table 3,
from 7.1 dynes/cm to below 1.0 dynes/cm; the spreading co-
efficient is increased from -1.1 dynes/cm to up to 5.6
dynes/cm. A typical nonionic surfactant, D4, is much less
effective.
- 74 -
10653Z7
Table 7
Effect of Anionic X~-Surfactant and its ~omolog Content
Example Nos. 45 to 50
Amphoteric Rf-Surfactant Solution Al: 4.93 % (30 % solids)
Anionic Rf-Surfactant . . . . Various: 0.29 %
Amphoteric Cosurfactant . . . . . C2: 8.33 % (30 ~ solids)
Other Amphoteric Cosurfactant . . C3: 1.66 % (70 % solids)
~onionic Cosurfactant . . . . . . D3: 2.97 % (70 % solids)
Solvent . . . . . . . . . . . . . El: 5.00 %
Water . . . . . . . . . . . . . Balance
Ex ~ple No. 45 46 47 40 ~9 50
Anionic Rf-surfactant, as noneB5 B6 B7 Bl B3
noted
Rf-homolog C6 CO C10 mixture mixture
Surface tension* dynes/cm 19.5 18.117.517.7 17.7 17-5
Interfacial tension* dynes/ 1.0 o.61.2 1.7 1.0 1.0
cm
Spreading coefficient* 4.1 5.9 5'9 5.2 5.8 6.1
dynes/cm
Film speed, sec very 13 5 38 9 5
slow
Resealing propertynone eoodgood poorgoodgood
*3 percent dilution in distilled water; interfscial tension against
cyclohexane
Table 8
Surface Properties of Amphoteric Rf-Surfactant/
Amphoteric Cosurfactsnt Solutions
Amphoteric Rf-Surfactant Solution . . . A5: 0.1 %
Cosurfactants - Variable . . . . . . . . . 0.1 ~
Water .......................... Balance
Surface Interfacial
Tension Tension Spreading
Example Cosurfactant dynes/cm dynes/cm Coefficient
51 none 18.6 7.1 - 1.1
52 C5 18.4 o.6 5.6
53 C6 18.8 o.6 5.2
54 C7 20.2 0.2 4.2
Cl 18.6 0.9 5.1
56 C8 19.3 0.5 4.8
57 D4 19.6 3.8 1.2
-
1065327
Examples 58 to 63
The AFFF agents having a composition as listed in Table
9 are identical with the exception that the nonionic aliphatic
cosurfactants of Type D vary. The comparison of the surface
tension and interfacial tension data show that almost identical
values within .5 of a dyne/cm are obtained and all samples
show excellent compatibility with sea water while the only
sample not containine nonionic hydrocarbon surfactant of
Type D shows a heavy precipitate if diluted with sea water and
aged at 65 C for 10 days.
- 76 -
10653'X7
Table 9
Composition and Evaluation Or ~FFF Agents
Example ~os. 58 to 63
Amphoteric Rf-Surfactant Solution A7: 4.93 % ~30 'h solids)
Anionic Rf-Surfactant. . . . . . . ~1: 0.29 %
Amphoteric Cosurfactant. . . . . . C2: 8.33 % (30 ~ solids)
Other Amphoteric Cosurfactant. . . C3: 1.66 % ~50 ~, solids)
Nonionic Cosurfactant. . . . .Various: 2.08 X (as 100 ~ solids)
Solvent. . . . . . . . . . . . . . El: 5.00 %
Water. . . . . . . . . . . , . . . . . Balance
_ _ _ _ .
Example No. ~ 58 59 60 61 62 63 .
Nonionic cosurfactant, as noted none D3 D5 C6 D7 D8
Surface tension* dynes/cm 18.0 17.3 17.4 17.0 16.9 17.5
Interfacial tension* dynes/cm 1.7 1.2 1.4 1.3 1.3 1.6
Spreading coefficient* dynes/cm 4.9 6.1 5.8 6.3 6.4 6.0
Compatibility with sea water heavy clear clear clear clear clear
6% dilution 65C for 10 days precipitate
.
*3 percent dilution in distil7ed \later; interfacial tension aga~nst
cylcohexane
10~53Z7
Examples 64 to 78
AFFF agents for 6 percent proportioning containing
2 percent by weight of variable solvents, but having otherwise
identical compositions as shown in Table 10 were evaluated by
using the Field Foam Test Method for determination of the
foam expansion of a 6 percent dilution of the novel AFFF
agents in synthetic sea water. As the data in Table 10 show,
it is possible to obtain expansion ratios ranging from
4.0 (high density foam) to 11.0 (lower density foam) by simply
varying the type of solvent used in the AFFF agent. It is
important from an ecological as well as economical standpoint
that such a wide foam expansion range can be achieved with such
a low (2 percent)solvent content.
10653'~7
~ o o o ~ CU o. o
~1 h
~ ~ O ~ ~ O
O ~ 00 0 0 ~
~i 0 ~) ~I N ~ ~o ~ o
........ ~ ~
~1 ~1 ~1 ~1 tt O ~1,J h O
~ O p~ bD r ~ ~
V~ I ~ ~ I N O
. ........ ~
: : : : : :
...... ~1
90 CO ~ Z ~ O ~- CO
. . O
~1 o . a ......... ~.. 1
,D ~ O ~1 Ul N O\ N ~1 ~ ~r) ~ u~
a o ." ........ o a
E~ ~o ~ ~ ......... ~ ~ o u~
o
~x ~ ~ ~
~1 ~ ~ ~ h X
~ o ~ 3 h ~
h h C~ ~ O ~ n
$.,t$ ~: ~ ~ ~ o .~ ~ ~
a ~ o g~ h ~ h ~I h O O c~
~ ~ ~ ~ Co,
Z u:~ :~ c~ ~h I ~ .~ ~h
~e; ~o ~o ~o ~o ~o ~
-79
10653'~'7
Ex _nles 79 to 82
AFFF agents having co~positions as shown in Table 11
were evaluated and compared with a co~mercial AFFF agent, Light
Water FC-200*, in 2.60 sq.m. fire tests. As the control time,
ext~nguishine time, and burnback time data show, superior
performance was achieved with the novel AFFF agents containing
down to one-half the amount of fluorine in the product, and
about equal control time, extinguishing time and burnback
time was achieved in comparison to FC-200 with the AFFF agent
Example 82 containing ~ust .8 percent fluorine vs. 2.1 percent
fluorine in FC-200. These results indicate the higher effi-
ciency of the novel AFFF agents, and that foam expansion is
not as important a criterion to performance as are superior
film properties.
*Trademark - 80 -
10~53Z'7
Table 11
Comparative Fire Test Data* of AFFF Agents
Example Nos. 79 to 82
. .
Amphoteric Rf-Surfactant Solution Al: Variable ( 30 % solids)
~onionic Cosurfactant . . . . . . Dl: Variable (100 % solids)
Al-~ 4 (solids basis)
Anionic Rf-Surfactant . . . . . . Bl: O. 35 % (100 % solids)
Amphoteric Cosurfactant . . . . . Cl: 2.25 %
Solvent . . . . . . . . . . . . . E2: 6.25 %
Water . . . . . . . . . . . . . . Balance
_
Example No. 79 80 81 82 FC-200
_ ~
Rf-surfactant A1, ~ as is 8.40 7.00 5.60 4.66
Nonionic surfactant Dl, % as i~ 1. 80 1.50 1.20 1.00
% F in formula 1.44 1.20 0.96 0.80 2.10
. .
Control time, sec 28 30 34 34 33
Extinguishing time, sec 44 34 47 51 52
Burnback time, min 8: 15 10: 30 5: 45 4: 58 5: 30
Foam expansion 5.5 5.6 5.4 4.7 7.0
25 % Drain time, min 4: 42 4 00 4: 15 3: 45 5: 03
* 6 ~ dilution in sea water, tested on 2.60 sq.m. fire
~ 81
10653'~7
Examples 83 to ô5
AFFF agents having the composition as sho~n in Table
12 with variable anionic Rf-surfactants of Type B and variable
solvents of Type E or containing no solvent at all were
evaluated in 2.60 sq.m. fire tests using 6.57 liters per
minute nozzle. As the test data in Table 12 show, high
density foams with a foam expansion of less than 5 and
as low as 3.7 are obtained with AFFF agents not containing
any solvent while a solvent content of 35 percent increases
foam expansion to as high as 8.5 with this AFFF agent
co~position. A comparison with the commercial FC-200 shows
th~t slightly better extinguishing times are obtained in
Example 83.
- 82
10653~7
0 ~P~P~ ~ ~. ~ Cq 0
O O ,~ ,t' ' 0 O O
~ ~: ~ a m~ co N
CO '-1 l _ Il~ 0 (r~ O
E~ ~ ~Qt ~ ~ ~ ;0
h ~ ~ +, ~ ~ C~
~ ~ ~ a 0 u~ s~
P q~ ~r7 ~ O
h h u ~Q ~n ~1 O ~ 0 O
~ t ~ ~ 1 1 to
s ~ a P ~ .3 ~ qt
~ æ ~ :~ z ~ ~~.1
~' ~= =~ a
q~ q~ ~ t ~ ~a h
a a CQ ~ ~ ~ ~
83
10~;53~7
Exam~les 86 to 90
AFFF agents having a composition as shown in Table
13 were evaluated in 260 sq.m.fire tests. The performance of
these AFTF agents containing different cosurfactants of Type
C show excellent control times (as low as 26 seconds), very
short extinguishing times (as low as 37 seconds), and two of
the compositions (Examples 88 and 90) did extinguish the fire
by itself shortly after removal of the pan used in the 2.60
sq.m. fire test, indicating the superior sealing capacity of
the novel AFFF agents in comparison to the commercial products
on the market.
- 84
10653Z7
Table 13
Compar~tive Fire Test Data* of AFFF Agents
Exa~ple Nos. 86 to 90
-
Amphoteric R -Surfactant Solution Al: 5.9 % ( 30% solids)
Anionic Rf-Surfactant . . . . . . Bl: 0.35% (100% solids)
Ionic (and Amphoteric) Cosurfactants . Variable
Nonionic Cosurfactant Dl: 1.2
Solvent . . . . . . . . . . . . . E : 6.o
Water . . . . . . . . . . . . . . Balance
_
Example No. 86 87 88 89 90
. _ .
Cosurfactant - 1% solids C3 C4 Cl Cl Cl
Cosurfactant - 2% solids C2 C2 C9 C10 C2
_
Control time, sec 26 27 33 33 26
Extinguishing time, sec 39 3~ 48 45 38
Burnback time, min 7:31 5:02 out 7:56 4:35 out
Foam expansion 5.9 6.2 6.7 5.9 6.6
25% Drain time, ~in 5:19 _ 5:20 5:05 5:55
*Tested as a 6% dilution in sea water on 2.60 sq.m fires
Fire completely extinguished
_ 85
10653Z7
Example 91
An AFFF agent ha~ing the composition as shown
in Table 14 was evaluated on a 117.05 sq.m. fire con-
ducted on a level circular area 12.19 m in diameter
fueled with 300 gallons of gasoline. A Rockwool FFF
nozzle with double screen uas used with a 189.27 1
per minute discharge. An excellent foam expansion of 9.0
was obtained and the fire was rapidly knocked down and almost
completely extinguished within the diked area. Burnback was
minimal and the "Su~mation of Percent Extinguishment" uas 320
far exceeding Mil Specifications F-24385 (Navy).
- 8~ -
106S327
Table 14
Fire Test of Preferred AFFF Agent on 117.0 sq.m Fire Test
Fxample No. 91
. _ _
Amphoteric Rf-Surfactant Solution Al: 5.93 % (30 % solids)
Anionic Rf-Surfactant . . . . . . Bl: O.35 %
Amphoteric Cosurfactant . . . . . C2: 10.00 % (30 % solids)
Other Amphoteric Cosurfactant . . Cl: 0.50 %
Nonionic Cosurfactant . . . . . . Dl: 1.20 %
Solvent . . . . . . . . . . . . . El: 6.oo %
Water . . . . . . . . . . . . . . . Balance
Surface tension* dynes/cm. . . . 17.0
Interfacial tension* dynes/cm . . . 1.4
Spreading Coefficient* dynes/cm . . . 6.2
Fire test performance as a 6 percent sea water dilution
Excellent knockdown and burnback
"Su~mation of Percent Extinguishment" - 320
Foam expansion tl89.27 1 per minute nozzle) 9.0
25 % Drainage . . . . . . . . . . . . . . . 4:00
50 % Drainage . . . . . . . . . . . . . . . 8:41
.
*3 % dilution in distilled water; interfacial tension
against cyclohexane
- 87
10~;5327
Example 8 92 to 96
AFFF agents having the compositions shown in Table
15 were tested as aerosol dispensed AFFF agents upon 2B fires
(Underwriters Laboratory designation). The results show
that the compositions were more effective in extinguishing
the fires in a shorter time than either of the commercially
available agents, Light Water FC-200 or FC-206. Example 94
shows that a composition protected against freezing iB also
effective as an extinguisher.
- 88
~0653'~
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-- 89
10653~7
Footnotes to Table 15
The % solvent content and % buffer salts are noted for the actual
aerosol charge after dilution of the concentrate to a 6% dilution;
the remainder is water
2The aerosol container is a standard can containing a 430 gram
charge of AFFF agent and a 48 gram charge of dichlorodifluoro-
methane
Buffer salts are Fl, Sorensen's phosphate at pH 7.5
F2, Sorensen*s phosphate at pH 5.5
F3, McIlva~ne's citrate/phosphate at pH 5.5
F4, Walpole's acetate at pH 5.5
6.o~ dilution in distilled water; interfacial tension against cyclo-
hexane
5discharge duration, sec - time to discharge aerosol completely at
21.1C
foam volume, liters - total foam volume immediately a M er discharge
control time, sec - time at which fire is secured, althougb still
burning
extinguishing time, sec - time for total extinguishment
62B fire - a 0.465 sq. meters area fire
*Trademarks - 90
iO653z~
Ex~mples 97 and 98
AFFF agents having the composition shown in Table
16 were compared to commercially available AFFF agents of both
6 percent and 3 percent proportioning types - 3M's Light
Water FC-206 and FC-203 and National Foam's Aer-0-Water*6
and 3. The Examples 97 and 98 both demonstrate vastly
superior film speeds (time to 50 percent seal), as well as
more complete and highly persistent seals than available
AFFF agents. These factors are of fundamental importance
for an effective AFFF composition.
*Trademark - 91
10653~
~able 16
Sealing Characteristics of AFFF Compositions
Example Nos. 97 and 98
Amphoteric Rf-Surfactant Solution A1: 5.0 % (30 % solids)
Anionic Rf-Surfactant . . . . . . Bl: 0.3 %
Amphoteric Cosurfactant . . . . . C2: 8.3 % (30 % solids)
Other Ionic Cosurfactants . . . . . . Variable
Nonionic Cosurfactant . . . . . . . . Variable
Solvent . . . . . . . . . . . . . El: 5.00 %
Water . . . . . . . . . . . . . . . . Balance
.
Aer-O-Water Aer-O-Water FC FC
Example No. 97 g8 6 3 206 203
. .
Cosurfactant Cl 0.4 --
Cosurfactant C4 -- 0.4
Cosurfactant D3 3.0 --
Cosurfactant Dl -- 2.1
Time to 50~ seal 5 8 18 18 25 12
% seal in 30 sec 98 97 45 30 85 72
% seal in 120 sec98 98 87 91 96 87
Surface area - 20 cm2
Delivery rate - 0.17 ml/min
Wave number _ 2930 cm 1
Cell path length - 3 cm
Helium flow rate - 1000 ml/min
- 92
10653~7
.
Examples 99 to 103
AFFF agents having compositions as shown in Table 17
were submitted to fish toxicity studies using fathead minnows
and bluegills. The evaluated AFFF agents have, as the results
show, considerably lower toxicity than the control (Light Water
FC-200) and, in addition, show a considerably lower chemical
oxygen demand than the control primarily because of the lower
solvent content in the novel AFFF agents.
93
10653Z7
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10653Z7
Examples 104 to 108
AFFF agents for 6 percent proportioning containing
different types of amphoteric cosurfactants of Type C and Type D
but with otherwise identical compositions, were evaluated. The
comparative evaluation data in Table 18 show (a) that 3 percent
solutions of the listed AF~F agents have spre~ding coefficients
ranging from 4.5 to 5.8 dynes/cm, and (b) that the concentrates
per se have a fish toxicity (fathead minnows) ranging from 114
to 524 ppm for a TL50, indicating that the listed AFFF agents
are considerably less toxic than Light Water FC-200, having a
TL50 of 79 ppm. Table 18 also shows that the listed AFFF agents
have considerably lower chemical and biological oxygen demands
(COD and BOD5) than FC-200.
- 95
10653~7
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- 9 1~ -
~ -
10653Z7
Example~ 109 to 113
Further optimized AFFF agents for 6 percent proportion-
ing containing different types and amounts of amphoteric and
nonionic cosurfactants of Types C and D, but identical a~photeric
and anionic Rf-surfactants of Types A and B, were evaluated. The
comparative evaluation data in Table 19 show that spreading co-
efficients ranging from 3.6 to 5.1 dynes/cm are obtained, while
fish toxicity data of the AFFF agent concentrates range from
294 to larger than 1000 ppm for a TL50 for fathead minnows.
A TL50 f larger than 1000 ppm is considered non-toxic ard
products like AFFF agents Examples 112 and 113 are therefore most
desirable from an ecology standpoint. Also listed in Table 19
are the chemic~l and biologica] oxygen demands (COD, BOD5) of
Examples 110 to 113. The very low COD Values ranging from 0.19
to 0.22 g. of oxygen per liter are primarily due to the low
solvent content in the novel AFFF agents.
~ ~7
~0653Z7
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_ ~8
10653Z7
Example 114
An AFFF agent having a composition as sho~m for
Example 112 and solutions thereof in synthetic sea water were
selected to show the low or non corrosive character of the novel
AFFF agents. Corrosion tests carried out in accordance with U.S.
military requirement MIL-F-24385 Amendment 8, June 20, 1974
show, as presented in Table 20, that corrosion observed with
different metals and alloys is 10 to 100 times smaller than the
maximum tolerance levels specified in MIL-F-24385, Amendment ô.
_ 99 _
10~;53,'~7
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-- 100 --
~O~;S3~7
EXamples 115 to 117
AFFF agents were formulated containing identical ingredients but at
progressively higher concentrations. The data show that concentrates can be
prepared for 3 percent, and even 1 percent proportioning, which are stable
5 and perform well. Six percent proportioning concentrates such as National
Foam, Aer-0-Water 6 and Light Water FC-200 containing 18 percent and 34 per-
cent, respectively, of sclvents, contain so much solvent that they could not
be formulated as 1 percent proportioning concentrates.
Table 21
Formulation of Highly Concentrated AFFF Agents
Example Nos. 115 to 117
. _
Example No.115 116 117
Proportioning Type ~ .3~ l 1~
_ % as is % solids % as is % solids % as is % solids
Amphoteric Rf-surfactant Al 3. 33 l . oo6.66 2.00 20.0 6. o
Anionic Rf-surfactant B2 0.80 0.20 1. 60 o .40 4. 80 1.20
Amphoteric cosurfactant C12 1.70 1. 703. 40 3. 40 10.20 10.20
Nonionic cosurfactant Dl 0.50 0.50 1.00 l.Oo 3.00 3.00
Solvent 6. oo __ 12.00 __ 36.00 __
Water 87. 67 __ 75.34 __ 26.00 __
Total 100.00 3.40100.00 6.30100 0020 40
Freezing point C -3 -7 -12
pH 7.5 7.5 7.5
Chloride content (ppm) ~5 '50 <5o
--101
