U.S. patent number 3,684,018 [Application Number 05/109,620] was granted by the patent office on 1972-08-15 for foam-forming flame-extinguishing compositions containing alkylpolyalkoxysulfates, polyoxyethylene resin and symmetrical dibromotetrafluoroethane.
Invention is credited to Pierluigi Fatutto, Nicolino Rainaldi.
United States Patent |
3,684,018 |
Rainaldi , et al. |
August 15, 1972 |
**Please see images for:
( Certificate of Correction ) ** |
FOAM-FORMING FLAME-EXTINGUISHING COMPOSITIONS CONTAINING
ALKYLPOLYALKOXYSULFATES, POLYOXYETHYLENE RESIN AND SYMMETRICAL
DIBROMOTETRAFLUOROETHANE
Abstract
A foam-forming flame-extinguishing composition containing an
aqueous solution of a water soluble alkylpolyalkoxy-sulfates,
preferably in combination with a polyoxyethylene resin and
advantageously, with symmetrical-dibromotetrafluoroethane.
Inventors: |
Rainaldi; Nicolino (Venezia,
IT), Fatutto; Pierluigi (Venezia, IT) |
Family
ID: |
26327322 |
Appl.
No.: |
05/109,620 |
Filed: |
January 25, 1971 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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827959 |
May 26, 1969 |
3609074 |
Sep 28, 1971 |
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83603 |
Oct 23, 1970 |
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Foreign Application Priority Data
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Jan 27, 1970 [IT] |
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19827 A/70 |
Jan 29, 1970 [IT] |
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19921 A/70 |
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Current U.S.
Class: |
169/43; 169/47;
252/3; 252/8; 252/8.05; 516/12; 516/14 |
Current CPC
Class: |
C08L
81/00 (20130101); A62D 1/0071 (20130101) |
Current International
Class: |
A62D
1/02 (20060101); A62D 1/00 (20060101); C08L
81/00 (20060101); A62d 001/00 () |
Field of
Search: |
;252/3,8.05,307,8
;169/1A |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
Polyox Water Soluble Resins, Union Carbide Company, New York, 1968
P. 1-4..
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Primary Examiner: Burnett; Robert F.
Assistant Examiner: Fritsch; D. J.
Parent Case Text
CROSS REFERENCE TO CO-PENDING APPLICATIONS
The present application is a continuation-in-part of our co-pending
application Ser. No. 827,959 filed 26 May 1969 (now U.S. Pat. No.
3,609,074, issued 28 Sept. 1971) and a continuation-in-part of our
application Ser. No. 83,603, filed 23 Oct. 1970 as a
continuation-in-part of application Ser. No. 827,959.
Claims
We claim:
1. A flame-extinguishing foam-forming composition comprising as
active fire-extinguishing components, 1,2-dibromotetrafluoroethane,
ammoniumlauryltriethoxysulfate and a polyoxyethylene resin, in
aqueous solution, of an average molecular weight of 250,000 to
8,000,000.
2. The composition defined in claim 1 wherein the ratio by weight
between said ammonium lauryltriethoxy-sulfate and said
polyoxyethylene resin ranges between 2 and 0.5.
3. The composition defined in claim 2 wherein said polyoxyethylene
resin has a viscosity in 0.5 to 5 percent aqueous solution of 5,000
to 8,000 cPs.
4. The composition defined in claim 3 wherein said polyoxyethylene
resin, said ammoniumlauryltriethoxysulfate and said
1,2-dibromotetrafluoroethane are present in an amount of 2 to 70
percent by weight of the composition.
5. The composition defined in claim 4 consisting essentially of 1
to 10 percent by weight of a 10 percent aqueous solution of
ammoniumlauryltriethoxysulfate, 1 to 10 percent by weight of a 0.5
to 5 percent aqueous solution of said polyoxyethlene resin, 2 to 70
percent by weight 1,2-dibromotetrafluoroethane, and 10 to 98
percent by weight water.
6. A method of extinguishing a hydrocarbon fire, comprising the
step of projecting the foaming composition defined in claim 5
thereupon.
Description
FIELD OF THE INVENTION
Our present invention relates to foam-forming flame-extinguishing
compositions and, more particularly, to flame-extinguishing
compositions particularly adapted to quench, extinguish or confine
fires fueled by hydrocarbons.
BACKGROUND OF THE INVENTION for
It has been proposed heretofore to extinguish fires by various
techniques based generally upon exclusion of oxygen from the
combustion site, abstraction of heat from the combustion site or
physical elimination of the flame from a fuel substance.
Considerable effort has been expended upon developing foam-forming
flame-extinguishing compositions of this purpose since the foam
functions as a mechanical barrier to the transport of oxygen to the
combustion site, covers the fuel to prevent or limit ignition, and
provides substances of high heat capacity for removal of heat from
the source of combustion. For the most part, such foam-forming
compositions have been found to require an aqueous medium, a
foam-stabilizing or foam-producing surfactant and a propellant.
However, such foam-forming flame-extinguishing compositions have
been inadequate for extinguishing fires fueled by hydrocarbons as
may develop at industrial installations, refineries, tank farms and
with the like, and burning hydrocarbons on water.
THE DISCLOSURE OF THE CO-PENDING APPLICATIONS
In the aforementioned co-pending applications, we have described
flame-extinguishing compositions constituting improvements over the
prior art systems and having greater foam stability, and ability to
extinguish fires on hydrocarbons more rapidly, the capability of
preventing flashback (i.e. re-ignition of a combustible substance
covered by the foam) etc.
In application Ser. No. 827,959, for example, we have described a
flame-extinguishing foam-forming liquid composition which contains
one or more fluorobromoalkanes in addition to the substances
commonly provided in flame-extinguishing foams. Such substances
included water, emulsifying and foam-stabilizing surface active
agents, propellants and foaming agents, antifreezing agents capable
of lowering the freezing point of the composition, buffering
agents, corrosion inhibitors and thickening and carrying agents.
The fluorobromoalkanes which were employed, in an amount of 5 to 25
percent by weight of the composition, were the bromine-containing
halogen-saturated alkanes of low carbon number, e.g. having one to
six carbon atoms in the main chain.
As pointed out in this application, best results are obtained with
compounds containing at least four fluorine atoms and at least two
bromine atoms per molecule and preference was given to
symmetrical-dibromotetrafluoroethane, 1,2-dibromo-1,1,
2,2-tetrafluoroethane. In that application, we have also pointed
out that the surface-active agents have been found to be most
suitable as the organic sulfonates and sulfates,
alkylarylpolyethyleneglycol ethers, esters of alcohol such as
sorbitol with higher fatty acids such as lauric, stearic, palmitic
acids, sodium or ammonium salts or sulfocarboxylic acids such as
dialkylsulfosuccinic acid with up to eight carbon atoms in each
alkyl group.
In our later application Ser. No. 83,603, we further pointed out
that the composition can be improved by associating with the
bromofluoroalkane a foaming agent of the ammonium
alkylpolyalkoxysulfate type to produce a binary combination with
the bromofluoroalkane. The binary combination, used as an aqueous
solution or dispersion, provided markedly improved results. It
appeared that the result is a consequence of some association of
the ammonium alkypolyalkoxysulfate and the bromofluoroalkane which
yields a more stable form (against heat and mechanical disruption)
than is obtainable when the bromofluoroalkane is used with other
foaming agents and also of greater stability than foams using the
ammonium polyalkoxysulfate in association with, say,
chlorofluoroalkanes in equivalent quantities. Equally surprising
was the fact that the improvement was particularly marked when the
fluorobromoalkane was the 1,2-dibromotetrafluoroethane mentioned
earlier. Best results were found to be obtained when the foaming
agent was ammoniumlaurylpolyethoxysulfate, the polyethoxy group
having two to 30 ethoxy units.
OBJECTS OF THE INVENTION
It is the principal object of the present invention to provide an
improved foam-forming flame-extinguishing composition capable of
rapidly extinguishing flames, especially of hydrocarbon fires, with
a minimum of flashback and a maximum of foam stability.
It is another object of the invention to extend the principles
originally set forth in the above-mentioned co-pending applications
to foam-forming flame-extinguishing compositions of an improved
nature.
SPECIFIC DESCRIPTION
We have now discovered, most surprisingly, that
alkylpolyalkoxysulfate in the form of water-soluble salts,
constitute excellent flame-extinguishing substances in their own
right, especially when dispersed as a foam upon a hydrocarbon fire.
Advantageously, the alkylpolyalkoxysulfate is used as an ammonium
salt, possesses ethoxy groups in a chain of two to 30 ethoxy groups
and has an alkyl group with eight to 22 carbon atoms, preferably
12-14. Best results are obtained with
ammoniumlaurylpolyethoxysulfate.
We have further found that ammoniumlaurylpolyethoxysulfate acts
synergistically or symbiotically with water-soluble high molecular
weight polyoxyethlene resins in creating flame-extinguishing foams
under the action of a blowing agent or propellant. Surprisingly,
the fire-fighting properties of a water-soluble surface active
substance capable of generating foam under the action of a blowing
agent, especially the ammoniumalkylpolyalkoxysulfate, are greatly
improved by the addition to the solution of the water-soluble
high-molecular weight polyoxyethylene resin.
We have found, moreover, that the flame-extinguishing activity of a
composition containing both the amoniumalkylpolyalkoxysulfate and
the high molecular weight polyoxyethylene resin is improved still
further by the addition of a symmetrical-dibromotetrafluoroethane
as a third active component.
It is self-understood that compositions of the present invention
may also contain propellants, dispersing agents and other
conventional adjuvants, such as corrosion inhibitors and
anti-freezing agents, in the amounts and of the type described in
the aforementioned co-pending application.
A preferred subgroup of water-soluble alkylpolyalkoxysulfate is the
ammonium salts of alxylpolyethoxy sulfuric acids in which the alkyl
radical contains 12 to 14 atoms in the main chain and the number of
ethoxy groups is two to 30 as noted earlier. Because the
ammoniumalkylpolyalkoxysulfates generally have peculiar foaming
characteristics, it has been found to be advantageous to use the
ammonium salt of lauryltriethoxysulfate, commonly in the form of a
water solution containing 10 percent by weight of the active
substance.
The polyoxyethylene resin is a polymer having 7,000 to 200,000
oxyethylene units per molecule, an average molecular weight of
250,000 to 8,000,000, and a viscosity of 5,000 to 8,000 cps in an
0.5 to 5 percent aqueous solution.
The liquid composition of the present invention may comprise the
three active components individually or in combination, together
making up 2 to 70 percent by weight of the composition, the balance
being water and adjuvants as noted earlier. When
ammoniumlauryltriethoxysulfate and the polyoxyethylene are used
together, they are present in a ratio by weight of 2 to 0.5 while
dibromotetrafluoroethane may be employed in an amount of 3.5 to 35
times the total weight of the ammonium salt and the polyoxyethylene
resin.
Preferably, the flame-extinguishing material has the following
composition:
1-10 percent by weight of a 10 percent aqueous solution of
lauryltriethoxysulfate;
1-10 percent by weight of a 0.5 to 5 percent aqueous solution of
polyoxyethylene resin of a viscosity between 5,000 and 8,000 cps
and an average molecular chain containing 7,000 to 200,000
oxyethylene units;
0-70 percent by weight 1,2-dibromotetrafluoroethane; and
10-98 percent water.
Substantially any technique may be used for dispensing the
composition of the present invention. The composition may be
projected onto the fire site with conventional foam-throwing
apparatus to which the components of the composition are fed
separately and are combined at the nozzle under the action of the
propellant or blowing agent. It has been found that, for practical
use in mobile fire-extinguishing installations, a mixture
containing an aqueous solution of ammoniumlaurylpolyethyoxysulfate
and the polyoxyethylene resin should be provided in one tank while
the dibrotetrafluoroethane is supplied in another tank, the
contents of the tanks being fed to the foam-projecting nozzle
together with a blowing agent such as carbon dioxide or one of the
other propellants set forth in the above-identified co-pending
application.
SPECIFIC EXAMPLES
EXAMPLE I
A rectangular metal container 8 .times. 5 meters, 25 cm deep, was
filled with water to a height of 10 cm; over this water layer 260
liters of gasoline and 140 liters of kerosene were poured.
The fuel was ignited and permitted to burn; after 60 seconds of
precombustion, a single operator began to extinguish the fire with
an aqueous foam-forming composition. The fire was completely
extinguished within 60 seconds.
The extinguishing composition was a 20 percent solution of foaming
agents based on ammoniumlaurylpolytriethoxysulfate, commercially
known as "METEOR-HIEX-MR-200," a trademark of Svenskaa
Skumslacknings A.B.
13.8 kg of this solution was used during the extinguishing of the
fire, projected from a tank of a mobile fire-extinguishing
installation through a normal fireman's nozzle together with 186.2
liters of water, at a pressure of 4 atm, under blowing with
air.
The expansion ratio (liters of foam generated by 1 liter of the
final aqueous solution, which is now 0.6 percent by weight in
ammoniumlauryltriethoxysulfate) was 1:10.
EXAMPLE II
Under the same operative conditions of Example I, after 40 seconds
of precombustion, the fire was completely extinguished within 50
seconds, with a fire-extinguishing composition prepared by
admixing, under blowing with air (expansion ratio 1:10 ) 2 volumes
of an aqueous solution consisting of:
1 volume of a 20 percent aqueous solution of foaming agents based
on ammoniumlaurylpolyethoxysulfate
1 volume of a 5 percent aqueous solution of a polyoxyethylene resin
having the molecular weight of 250,000 to 8,000,000 and the
viscosity range from 5,000 to 8,000 cPs (this solution is
commercially known as "POLYOX-WRS-750", a trademark of the Union
Carbide Company)
20 volumes of water.
The consumption of the aqueous solution was 4.1 liters (plus 410
liters of water).
EXAMPLE III
Example I was repeated, but with a mixture of 400 liters of
gasoline and 100 liters of kerosene as the fuel. The fuel was
ignited and let burn for 60 seconds; after this precombustion
period, the fire was put out within 23 seconds, using the following
liquid composition:
a) 1,2-dibromo-1,1,2,2-tetrafluoroethane kg16 (propelled from a
separate tank of the mobile fire-fighting installation b) an
aqueous solution kg0.86 consisting of 1 volume of a 20% aqueous
solution of foaming agents based on ammonium
laurylpolyethoxysulphate 1 volume of a 5% aqueous solution of
polyoxyethylene resin (propelled from a separate tank of the mobile
fire-fighting installation) c) water kg8.6
The flame-extinguishing composition was blown under pressure with
air, maintaining an expansion ratio of 1:10.
EXAMPLE IV
Example 3 was repeated.
After 60 seconds of precombustion, the following liquid
composition:
a) 1,2-dibromo-1,1,2,2-tetrafluoroethane kg8 b) aqueous solution of
the two components cited in Example III, 1:1 by volume kg2.2 c)
water kg22
extinguished the fire within 22 seconds (expansion ratio, as
previously defined, 1:10).
EXAMPLE V
Example III was repeated.
After 60 seconds of precombustion, the fire was put out within 32
seconds using the following mixture:
a) 1,2-dibromo-1,1,2,2-tetrafluoroethane kg24.4 b) 20% aqueous
solution of foaming agents based on ammonium
laurylpolyethoxysulphate kg7.11 c) water kg110.
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