U.S. patent number 3,849,315 [Application Number 05/254,404] was granted by the patent office on 1974-11-19 for film-forming fire fighting composition.
This patent grant is currently assigned to National Foam System, Inc.. Invention is credited to Peter Jordan Chiesa, Jr..
United States Patent |
3,849,315 |
Chiesa, Jr. |
November 19, 1974 |
FILM-FORMING FIRE FIGHTING COMPOSITION
Abstract
Aqueous foam film-forming fire fighting compositions based on
mixtures of fluorocarbon and siloxane surfactants, are improved for
sub-surface introduction into burning hydrophobic liquids by the
addition of a different surfactant that increases foamability and
has a hydrophilic moiety weighing at least 80 percent more than its
lipophilic moiety.
Inventors: |
Chiesa, Jr.; Peter Jordan (Penn
Township, Chester County, PA) |
Assignee: |
National Foam System, Inc.
(West Chester, PA)
|
Family
ID: |
22964185 |
Appl.
No.: |
05/254,404 |
Filed: |
May 18, 1972 |
Current U.S.
Class: |
252/3; 556/423;
252/8.05; 516/12; 516/15; 516/914; 516/906 |
Current CPC
Class: |
A62D
1/0085 (20130101); Y10S 516/906 (20130101); Y10S
516/914 (20130101) |
Current International
Class: |
A62D
1/02 (20060101); A62D 1/00 (20060101); A62d
001/00 () |
Field of
Search: |
;252/3,8.05,307,310,311-312,357 ;260/448.2R,448.2N,309.6 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Weinblatt; Mayer
Attorney, Agent or Firm: Connolly and Hutz
Claims
What is claimed is:
1. In an aqueous film-forming fire-fighting foamable liquid
containing dissolved fluorocarbon and silicone surfactants in
amounts that give the liquid a surface tension at least as low as
19 dynes per centimeter but do not give it good foamability and
also containing one or more foamability-increasing surfactants that
are neither fluorocarbons nor silicones, to bring the foamability
of the liquid up to the level needed for a fire-fighting foam, the
improvement according to which at least 40 percent of the
foamability-increasing surfactants is an imidazoline or amine
di-propionate surfactant with hydrophilic and lipophilic moieties
of which the hydrophilic moiety has at least three hydrophile units
selected from the class consisting of hydroxyl, carboxyl, sulfo and
nitrogen, and weighs at least 80 percent more than the lipophilic
moiety.
2. The combination of claim 1 in which the lipophilic moiety is in
the form of a hydrocarbon chain not over 10 carbons long.
3. The combination of claim 1 in which the imidazoline has one of
its ring nitrogens quaternized with two carboxylated carbon chains
each having not over two hydrophobic carbons connected
together.
4. The combination of claim 1 in which the hydrophilic moiety
weighs at least 120 percent more than the lipophilic moiety.
5. The combination of claim 1 in which the imidazoline surfactant
is: ##SPC5##
where R is a C.sub.7 to C.sub.9 alkyl, and the amine di-propionate
surfactant is C.sub.8 H.sub.17 N(CH.sub.2 CH.sub.2 --COONa).sub.2
or ##SPC6##
6. In the method of fighting a fire in a body of liquid hydrocarbon
held in a container by introducing an aqueous foam into the body of
liquid from a location below the surface of that body, the
improvement according to which the aqueous foam is the foamed
composition of claim 1.
7. In the method of fighting a fire in a body of liquid hydrocarbon
held in a container by introducing an aqueous foam into the body of
liquid from a location below the surface of that body, the
improvement according to which the aqueous foam is the foamed
composition of claim 4.
Description
The present invention relates to fire fighting, and particularly to
the use of film-forming compositions in the fighting of fires.
Application Ser. No. 131,763 filed Apr. 6, 1971, discloses aqueous
foam compositions that spread films over hydrophobic liquids and in
this way extinguish flames on such liquids. While those
compositions do an admirable job in controlling fires in
hydrophobic liquids, even when the foams do not cover the entire
burning surface, one of the objects of the present invention is the
provision of even more effective fire fighting film-forming
compositions and methods.
The foregoing as well as additional objects of the present
invention will be more completely understood from the following
description of several of its exemplifications.
It has been discovered that the fire-fighting compositions of
application Ser. No. 131,763, the contents of which application are
incorporated herein as though fully set forth, are improved by
substituting for at least about 40 percent of the
foam-ability-improving surfactant, one that has a hydrophilic
moiety whose weight is at least 80 percent greater and better still
at least 120 percent greater than the weight of its lipophilic
moiety. In other words, in an aqueous film-forming liquid
containing dissolved fluorocarbon and silicone surfactants in
amounts that give the liquid a surface tension at least as low as
19 dynes per centimeter but do not give it good foamability,
improvement is made pursuant to the present invention by having the
liquid also contain a different surfactant that has a hydrophilic
moiety whose weight is at least 80 percent greater and more
desirably at least 120 percent greater than its lipophilic moiety,
and is contained in an amount at least about 40 percent of that
which provides good foamability to the liquid.
Preferred lipophilic moieties for the last mentioned surfactant are
hydrocarbon chains not over 10 carbons long, or better still only 7
or 8 carbons long. Also the best hydrophilic moieties contain at
least 3 hydrophile units such as hydroxyl, carboxyl, sulfo and
nitrogen. Particularly effective surfactants are those of the
imidazoline type containing a quaternized nitrogen hydroxide
carrying two short carboxylated chains. Others falling within the
foregoing definition and providing very good results include
disodium n-octyl amine di-propionate.
A feature of the present invention is that the fire-fighting foams
thus produced are very effective for extinguishing fires in burning
hydrophobic liquids by introducing the foam into the burning liquid
below the liquid's surface. Such sub-surface introduction is a
particularly desirable technique for fighting fires in storage
tanks, for example, inasmuch as less vulnerable and less expensive
foam-supplying installations can be used.
The fire-fighting composition of the present invention can also
contain other ingredients such as anti-freeze agents, hydrophilic
resins, buffers, sequestering agents such as those for the cations
of sea water, preservatives, the acetylene glycols of Ser. No.
131,763, etc. The new composition can also be prepared from
concentrates which are diluted with tap or sea water when needed to
be applied to a fire.
The following examples show typical compositions pursuant to the
present invention.
EXAMPLE I
55 grams (CF.sub.3).sub.2 CF(CF.sub.2).sub.n
COO.sup.-.sup.+NH.sub.3 C.sub.2 H.sub.5 where n is 4, a minor
amount of which can be replaced by compounds where n is 2, 6 and
8,
128 grams of a 40 percent by weight solution in 1:1 by volume
water-isopropanol, of ##SPC1##
a minor amount of which can be replaced by compounds in which the
bracketed portion occurs 2, 4 and 5 times, rather than three,
400 ml of a 48 percent by weight solution in water of ##SPC2##
215 ml of a 10 percent by weight solution in water of the
condensation product of 3-dimethylamino-propylamine-1 with an
equivalent amount of an ethylene-maleic anhydride copolymer having
3 molar proportions of ethylene for every mol of maleic acid and
having a viscosity of 7 cps. at normal pH as a 2 percent solution
in water, a softening temperature of 170.degree.C. and a melting
temperature of 235.degree.C. The condensation reaction which is
slightly exothermic takes place in water solution at room
temperature and opens each acid anhydride group to make one
carboxyl and one amide of 3-dimethylamino-propylamine-1,
340 ml diethyleneglycol monobutyl ether,
20 g tris hydroxymethylamino methane, and
water to make 1 gallon.
The foregoing ingredients are mixed in any order and the final
product is a so-called 6 percent fire-fighting concentrate. It can
be stored for many months, and is used for fire-fighting by mixing
it with 162/3 times its volume of water and also with sufficient
air to foam with an expension of 3 to 6. This expansion is
generally considered adequate for fire fighting. Such mixing is
conveniently effected with a high-back-pressure venturi as shown in
U.S. Pat. No. 3,475,333 granted Oct. 28, 1969, for sub-surface
introduction into the usual types of storage tanks.
EXAMPLE II
68 g of the fluorocarbon surfactant of Example I,
127 g of the same 40 percent solution of silicone surfactant
described in Example I,
370 ml ethylene glycol,
467 ml of a 30 percent by weight aqueous solution of about a 1:1
mixture of sodium n-octyl and n-decyl sulfates,
467 ml of a 28 percent by weight aqueous solution of ##SPC3##
31 g tris hydroxymethylamino methane,
6 g sodium nitrilotriacetate,
340 ml diethylene glycol monobutyl ether, and
water to make up 1 gallon.
This mixture can be used interchangeably with that of Example I,
but by reason of the sequestering action of the nitrilotriacetate
it works better than that of Example I when diluted with sea
water.
The silicone surfactant is somewhat more stable in a solution that
contains isopropyl alcohol. It is accordingly helpful to increase
the amount of isopropyl alcohol in the 6 percent concentrates of
Examples I and II. As much as 5 percent by weight isopropyl alcohol
can thus be present in those concentrates. Larger concentrations
are undesirable inasmuch as they tend to unduly lower the flash
point of the concentrates. The silicone surfactants are also more
stable if kept from acid media and as in Ser. No. 131,763 a pH of
about 7.8 is preferred for the concentrates of the present
invention. The tris hydroxymethylamino methane helps buffer the
concentrates of the foregoing Examples at about that pH, even when
they are mixed with other concentrates that are acid. There is
however no need to preserve the pH when the concentrates are
diluted for application to a fire inasmuch as the diluted
fire-fighting liquid does not lose any significant fire-fighting
ability if it is on the acid side for the relatively few minutes
needed to control the fire.
Any of the fluorocarbon surfactants disclosed in Ser. No. 131,763
can be used in place of those of Examples I and II. Other anionic,
cationic or amphoteric fluocarbon surfactants such as those shown
to be effective in U.S. Pat. No. 3,655,555, granted Apr. 11, 1972,
can also be so used. Similarly any of the silicone surfactants of
that prior application can be used in place of those of Examples I
and II. A fungicide such as formaldehyde or the sodium salt of
o-phenyl-phenol can also be added to the concentrates to inhibit
mold growth and the like.
The concentrates of the present invention can also be prepared for
dilution in proportions other than the 162/3:1 ratio given above.
Another widely used dilution ratio is 331/3:1 and for such use the
concentrates can be prepared to have double the strength shown in
Examples I and II. Other dilutions take correspondingly modified
concentrates, although it is not necessary to accurately proportion
the dilution. As much as a plus or minus 50 percent departure from
the target dilution proportion can be tolerated. One reason for
such tolerance is that the fire-fighting effectiveness of the
diluted mixtures is not dependent to any significant degree on good
foaming. Even a foam of the present invention with an expansion of
2 will do a good job of rapidly extinguishing a gasoline fire by
subsurface introduction.
It will be noted that in the foregoing Example II the imidazoline
surfactant is so effective that it is diluted with more than an
equal amount of less effective surfactant composition outside the
scope of the present invention. That example can be substantially
improved by replacing the less effective surfactant composition by
an additional quantity of the imidazoline surfactant of Examples I
or II, or any other imidazoline surfactant such as ##SPC4##
In the foregoing surfactants the long unsubstituted alkyl chain of
7 to 9 carbons is the lipophilic moiety. The balance of the
molecule is the hydrophilic moiety and contains a multiplicity of
hydrophile units. The quaternary hydroxylated nitrogen is one such
unit, the other nitrogen is a second, and the alcohol, carboxy and
sulfo groups are additional ones. A chain of two carbons will not
detract from the hydrophilic character even if such chain is fully
hydrogenated and also carries a methyl branch. Oxygen or nitrogens
should therefore interrupt carbon chains to leave chain lengths not
more than two carbons long. Thus the two carbons connected together
in the imidazoline ring are counted as part of the hydrophilic
moiety, as is the CH.sub.2 CH.sub.2 OCH.sub.2 portion of the
imidazoline of Example I. Similarly the ring carbon to which the
lipophilic moiety is connected has two nitrogens also directly
connected to it and for that reason is considered part of the
hydrophilic moiety.
In place of the imidazoline type surfactant of Examples I and II
there can be used the di-sodium, di-potassium or mixed
sodium-potassium salt of n-octyl amine di-propionic acid, e.g.,
C.sub.8 H.sub.17 N(CH.sub.2 CH.sub.2 --COONa).sub.2, or the
corresponding salts of n-octyl amine di-2-methyl propionic acid
although they are somewhat less effective. Because of the
prohibitive expense it is impractical to use a fluorocarbon or
siloxane type surfactant as a foamability-improving material.
Obviously many modifications and variations of the present
invention are possible in the light of the above teachings. It is,
therefore, to be understood that within the scope of the appended
claims the invention may be practiced otherwise than as
specifically described.
* * * * *