NL8003291A - FIRE EXTINGUISHER, WHICH PROVIDES AN AQUEOUS FILM-FOAMING FOAM, AND A CARTRIDGE FOR IT AND METHOD FOR EXTINGUISHING FIRE WITH SUCH FOAM. - Google Patents

Description

¢ - * i TO 0547 t * 1 Fire Extinguisher, which provides an aqueous film-forming foam, cartridge therefor, and method for extinguishing fires with such a foam.

The invention relates to a hand portable fire extinguisher, which provides an aqueous film-forming foam, to a cartridge therefor, and to a method of extinguishing fires with such a foam. The invention also relates to a mixture of a water-soluble, fluorine-containing, aliphatic, surfactant and a water-soluble fluorine-free surfactant, as well as objects formed from said mixture. The invention relates to a method for extinguishing a fire of a flammable liquid, or to preventing such a fire, by applying a foam of a hand-held fire extinguisher to the surface of that liquid. aqueous film-forming solution.

One of the most effective foam-forming agents for extinguishing fires from flammable liquids, such as fuel fires, is an aqueous film-forming solution that contacts fires in the form of a foam (which in America is commonly abbreviated as "AFFF"), while a commercial fire extinguishing agent of this type is one sold as an aqueous liquid concentrate under the trade name "Light Water" (registered trade mark). After dilution with water, this agent has been successfully used to extinguish a large number of pilot fires and actual fires, such as petrochemical storage fires, 3-day oil tanker fires, jet fires and numerous industrial spills. and solvents.

Compositions of surfactants which can be used in or as fire-fighting agents, including those of the AFFF type, are e.g. described in U.S. Pat. Nos. 3,258,423, 3 * 562,156, 3,661,776, 3,772,195, 3,957,658, 4,090,967, and 4,149 * 599 * 3, these 800 32 91 - 2 mixtures consist of solutions of a water-soluble, fluorine-containing aliphatic surfactant, a water-soluble fluorine-free surfactant and water. When applying these mixtures with, for example, a foam or water / mist producing device, a foam is developed which spreads over the surface of the burning liquid, such as gasoline, and flows over that surface, forming a vapor barrier film to extinguish the fire; the film also protects the 10 non-burned areas and prevents ignition. These mixtures are usually supplied and stored as aqueous concentrates which, when used, are further diluted with water or can be stored in dilute form, AFFF fire suppression systems are e.g. used to prevent and control fires of relatively very dangerous or potentially dangerous flammable liquids and require a specially designed dosing and dispensing device which functions by mixing the required amount of concentrate with water to form the foam .

Recently, hand-held AFFF fire extinguishers are commercially available, such as the 3M "Spoiler" fire extinguisher, described in the 3M bulletin Y-FEBIR (1062) MP, which has been deployed and can be used to control relatively small amounts of flammable liquids, such as can commonly be found in automobile garages, paint shops, etc. These fire extinguishers are specially designed and contain approximately 9.5 liters of pre-mixed AFFF ready to use and are suitable for fighting small fires of "class B" and "class A".

Briefly, an embodiment of the invention relates to a hand-portable fire extinguisher, consisting of a water-pressurized tank, a pinch handle and valve-mounted mount located on top of the tank 800 32 91 * - 3 - and "preferably includes a locking pin and a pressure gauge, a dispensing hose connected to the valve mount and terminated in a nozzle, and a cartridge holder connected to the hose upstream of the nozzle and containing a cartridge consisting of from a formed solid body having at least one exposed surface and containing a solid water-soluble, coalesced mixture of a water-soluble, fluoroaliphatic surfactant and a compatible water-soluble, fluorine-free surfactant which extinguisher, upon activation, functions by draining water from the tank via said cartridge holder, which k comes into contact, said surfactants dissolving and providing via the nozzle a foam of an aqueous film-forming foam ("AFFF") solution of relatively constant composition which can be administered to a flammable liquid to extinguish a fire thereof (ie a "class B" fire), or to prevent such a fire by forming a tough, resistant, rapidly forming and spreading aqueous film on the surface of the flammable liquid, generally on the manner described in the aforementioned patents.

The extinguisher according to the invention can also be used to combat a fire of a solid fuel, such as paper and wood (ie a "class A" fire) more effectively than by a conventional hand-portable 9 »5 liter water-containing fire extinguisher. Such a conventional extinguisher, as described below, can be easily converted into an extinguisher according to the invention to combat both classes of fires.

The cartridges used in the fire extinguishing systems according to the invention may consist of a single-shaped body containing the mixture of solid surfactants. In one embodiment of the cartridge construction 35, e.g. the mixture of solid surfactants 800 3 2 91 - 4 - in the form of a layer, with or without a reinforcing matrix (eg, a layer of needlefelt), which is laid on a non-woven water-insoluble water -permeable textile product, in which the whole is rolled up as a roll and when a cartridge is arranged in a sleeve, and the filled sleeve is placed in a cartridge holder, More particularly the mixture of solid surfactants can be heated and pressed, cut to size, placed in the correct direction on a piece of nonwoven fabric, heated to soften it, rolled up and patterned into a sleeve. In another example, the molded body containing the solid surfactant mixture is in the form of a single solid cylinder with a star-shaped axial channel for water passage. In yet another embodiment, the cartridge is a water-permeable assembly of a plurality of (e.g., 50-20,000) shaped bodies (containing said solid surfactant mixture) in the form of discrete pellets, beads, bars, etc. 20 attractively equal in size and shape, the water permeability of the assembly being due to the interstices between the many shaped pills, etc., which provide channels for the water that has flowed through the cartridge.

These types of cartridges, which are formed by one or more shaped bodies of the solid surfactant mixture, provide an aqueous film-forming solution of relatively constant composition as the surfactant mixture dissolves in the water stream supplied from the tank . The total active surface of the shaped body or shaped bodies of the surfactant mixture is a predetermined active surface sufficient to provide the AFFF solution with the required relatively constant composition at a given discharge rate. The aforementioned predetermined active surface will vary depending on the "particular solid mixture of surfactants, the manufacture and the nature and composition of the molded body or molded bodies, the number, shape and size of these bodies, and the volume, rate of discharge, and temperature of the water in the tank. "Relatively constant composition" means that the minimum concentration of the surfactants in the resulting solution during the discharge period of the fire extinguisher is at least about 50%, preferably at least 55% of the maximum concentration.

To ensure this required composition, the amount of the shaped body or shaped bodies of the cartridge is such that generally a residual amount of the shaped body or shaped bodies will remain in the cartridge holder after all of the water from the tank has been drained.

In the accompanying drawings: Fig. 1 shows a view of an embodiment of a fire extinguisher according to the invention, provided with a filled cartridge holder; FIG. 2 is a longitudinal sectional view of the mouthpiece of the loaded cartridge holder of FIG. 1; fig. 3 shows a perspective view of an embodiment of a preform or intermediate product of a cartridge, which shape or product can be rolled up and placed in the cartridge holder of fig. 2; and FIG. 4 is a front perspective view of a cartridge assembled from the preform of FIG. 3.

In the drawings and in the first place in Fig. 1, the number 1 represents an embodiment of a hand-portable fire extinguisher according to the invention, comprising a tank 2, on which a pinch handle 3 »a pressure gauge 4, a tilt (not visible ) and a locking pin 6 is mounted, this combination being connected to a delivery hose 7j 35, the end of which is connected to a cartridge holder 8, which is connected 800 3 2 91 - 6 - to an air suction nozzle 9 · A conventional portable water fire extinguisher of class A (containing eg about 9 liters of water and about 2.8 liters of compressed gas, eg air or nitrogen) can be easily modified for the purposes of the invention by changing the nozzle thereof, which flows directly remove and replace this nozzle with the combined cartridge holder and nozzle assembly, as shown in Figures 1 and 2. Also, a conventional fire extinguisher can class A are modified by cutting the conventional delivery hose therefrom, placing a cartridge holder according to the invention between the cut ends, attaching the cartridge holder to the cut ends of the hose with suitable clamps or the like and replacing the usual nozzle with an air-intake nozzle.

Fig. 2 represents an embodiment of a filled cartridge holder according to the invention, in which a cylinder consisting of parts 10 and 11, which parts are to be screwed together, e.g. by means of straight ("straight") or spiral trapezoidal threads, as described in NASA Tech Brief 71-10336 (September 1971) »of an internal cartridge chamber 12 (eg, with a volume of about 250 cm ^) provided such that the sleeve 20 can contain a cartridge 13 according to the invention, the upstream end of cylinder part 11 having a fitting 5 to which the downstream end of hose 7 can be connected, while the the downstream end of the cylinder part 10 can be connected to an air-suction nozzle 9, the upstream end of which is provided with air openings 15 and with a control valve 16 to prevent fluid, eg moist air or water, flows through the nozzle into the cartridge holder. The exterior of the cartridge holder may be grooved, as shown in the figure, to enable the operator to hold the container-nozzle combination during discharge 800 3 2 91 - 7 ft. hold the extinguisher firmly.

In Fig. 3, a pattern preform or intermediate 13 'is shown, consisting of a flat, rectangular porous substrate 21, on which a molded body 22 of said 5 fluorine-containing aliphatic and fluorine-free surfactants is placed in the mold of a slightly smaller, flat, rectangular layer, which is offset from one end and the sides of the substrate 21, while the other end of the layer 22 coincides with the other end of substrate 21. When the preform 13 'of Fig. 3 is coiled around itself, it assumes the spiral or roll form 13 shown in Fig. 4, the final winding of substrate 21 forming the outer wall of the roll. Assembled in this manner, cartridge 13 can be mounted in a sleeve 15 (which can be considered part of the cartridge), which is made of plastic, metal, cardboard, phenolic resin impregnated paper, etc. and are placed in the cartridge chamber 12 of the cartridge colder 8 of Fig. 2, the porous substrate 21 serving both to separate the parts of the surface of the molded body 22 and to provide channels, thereby water can flow to come into contact with said surfaces as it flows from the tank to the nozzle. If desired, as shown in Figures 3 and 4, a second short porous substrate 23 may be placed on one end of the formed body 22 to provide a central channel when the preform 13 is coiled around itself.

In operation, fire control is achieved by removing the locking pin 6, squeezing the handle 3, opening the valve and entering the pressurized water through hose 7. the cartridge holder 8 can flow and a foam can be dispensed through nozzle 9 from an "AF ??" solution of relatively constant composition, namely a foam of an aqueous film-forming foam solution, which is generally 0 0.05-1 wt.% Fluorine- 800 3 2 91-8 - aliphatic surfactant, wherein the weight ratio of fluoroaliphatic surfactant to fluorine-free surfactant is 10: 1 to 1:25. As it flows through the cartridge holder, the water passes through the channels formed by the porous substrate 21, 23, in contact with the surface of the formed body 22 and dissolving the mixture of surfactants. The active area of the shaped body 22 and the rate at which each component 10 is dissolved are relatively constant during the discharge period. The 9> 5 liters of water will be delivered in 45-90 seconds with an initial pressure of approximately 686 kPa. The extinguisher can be refilled with about 9 liters of water and about 2.8 liters of compressed gas and after drying the cartridge holder with a new cartridge, if the cartridge used is a single-shaped body, the cartridge can be manufactured in many other forms, as long as the active surface of the formed surfactant body exposed to the water flow from the tank does not significantly change during dissolution of the surfactant, for example, the formed The body may be a solid cylinder with an axial channel, which has the shape of a star in cross-section, the wall of the channel being exposed to the water discharged from the tank In such an embodiment, usually no porous substrate will be required.

Rather than filling the cartridge holder with a cartridge consisting of a single-shaped body of the solid surfactant mixture, the cartridge may contain, as described above, a water-permeable assembly of a plurality of shaped bodies, e.g. pills, the active surface of which becomes smaller during dissolution. For example, cartridge 13 of Fig. 2 can be replaced by an assembly of more than one such shaped body. The sleeve 20, at least at the downstream end, may be provided with a suitable liquid. permeable or porous end cap, such as one or more discs, which are made from an open, non-woven web of low density, such as e.g. disclosed in U.S. Pat. Nos. 2,958,593 and 3,537,121, which are commercially available under the trademark "Scotch-Brite". Such discs may, if desired, be secured in place, circumferentially to the sleeve, for example, by a friction fit or with a water-insoluble adhesive, eg a room temperature vulcanisable ("RTV") silicone rubber Such end caps will retain the assembly in the sleeve during handling and during dissolution during operation.

When using more than one molded body, this can be accomplished by bringing the solid mixture of surfactants to the required size and shape by extruding or pelleting the solid mixture. In order to maintain channels for the water passage through a cartridge made from such shaped bodies, they are preferably made into spherical or pole-flattened shapes, ie bodies with substantially round or curved surfaces.

The shaped body or bodies of the surfactants used according to the invention, e.g. layer 22 of FIGS. 3 and 4 consists of a solid coalesced mixture of one or more water-soluble fluorine-containing aliphatic surfactants and one or more compatible water-soluble fluorine-free surfactants. The mixture is usually solid at ambient temperature and does not liquefy at temperatures below about 50 ° C.

The fluoroaliphatic surfactant compound contains one or more fluorinated aliphatic residues (R ^) and one or more water-solubilizing polar groups (z), which are usually bonded by suitable linking groups (Q).

80032 91 P- y * ** * - -10-.

Particularly suitable fluoroaliphatic surfactants are those described in U.S. Pat. No. 3,556,156. The particular structure of the fluoroaliphatic surfactant is not critical; rather, suitability for the intended purpose is determined by the balance of the physical properties of the compound. It is necessary that the combination of the fluoroaliphatic moiety and the water-solubilizing group is equilibrated such that the surfactant at 25 ° C achieves a water solubility of at least 0.01 wt.%. It is preferred that the water solubility be at least about 0.25 wt%. The surfactant should be surfactant enough to provide a surface tension in aqueous solution at a concentration of about 0.25% or less, less than about 280 micronewton / ca, preferably less than 230 micronewton / ca.

If the fluoroaliphatic surfactant is too soluble in a hydrocarbon liquid, it will be extracted from the aqueous film too quickly to provide a sufficiently durable coating. Generally, in the surfactant, this requires the presence of at least about 20 weight percent fluorine, i.e., carbon bonded fluorine. A fluorinated aliphatic residue with these properties can generally be described as a fluorinated, saturated, monovalent, non-aromatic residue of at least 3 carbon atoms. The aliphatic chain can be straight, branched or, if sufficiently large, also cyclic and may also contain exclusively oxygen or trivalent nitrogen atoms attached to carbon atoms. A fully fluorinated radical is preferred, but hydrogen or chloro-octa can be present as substituents provided that no more than 1 atom of each is present on every two carbon atoms, while the residue preferably contains at least one terminal perfluoromethyl group. While residues with 800 32 91 t * - 11 - will function adequately a greater number of carbon atoms, compounds with no more than about 20 carbon atoms are preferred, since larger residues usually mean less efficient utilization of fluorine than with shorter chains. 5 tens is possible. Most preferred are di-aliphatic radicals having about 5-Ί2 carbon atoms.

The water-solubilizing polar group may be an anionic, a cationic, a nonionic or ampholytic moiety or may consist of combinations thereof. Examples of anionic groups include CO 2 H, COgM, SQgM, SO 2 S, SO 2 M, 0P (0i) 2 and 0P (0M) 2, wherein M represents a metal ion such as sodium, potassium, calcium, etc. Examples of cationic groups are II, EER, where E is a lower alkyl group, such as methyl, ethyl or butyl, ER '^ A', where H 'represents a lower alkyl group or hydrogen and A' is an anion, such as chloride, sulfate, phosphate, hydroxyl, etc. Examples of non-ionic groups are -11- ^ 0 and those derived from polyethylene oxide and mixed polyethylene oxide-polypropylene oxide polyols. Examples of mixed or ampholytic groups are -ΪΤ ^^ ΟΞ) 2, -NEC ^ NHC ^ NHj, -E + (CH3) 2C2H4CO ·, / ”li + (CH3) 2G2H4C0OITa_70H ', -27 (0 ^) (0 ^ 00 ^) -5> 0, and the like.

The linking group is a polyvalent, generally divalent linking group, such as alkylene, arylene, sulfonamidoalkylene, carbonamidoalkylene, and the like. In some cases, more than one fluoroaliphatic moiety may be linked to a single linking group and in other cases, a single fluoroaliphatic moiety may be linked to more than one linking group or may be linked by a single linking group to more than one polar solubilizing group.

A particularly suitable class of fluoraiiphatic surfactants which can be used according to the invention are those corresponding to the formula 35 (RJ (Q) 2, wherein Rf is said fluoraiiphatic residue, X II mx 800 32 91 - 12 - n = 1 or 2, Q represents said linking group, m is an integer from 0 to 2 and Z represents said water-solubilizing group.

Representative fluoroaliphatic surfactants which can be used in the method of the invention are:

WV

CiF1, S02lf (CH20HOHCa2S0j) C3H6H + (CE,) 2C2H.0E

CgP ^. ^ SOjHECE ^ gE ^ O ^ a 10 CQP S02BHC6H4S0 Yes C6Fi3S02ir (c3H6S03) C3H6ir + (CH3) 2C2H40BC 0? P15COITHC3H6ir2 (CH3) 2C2H4C00 'C8F17C2H2C2H2SC2H2SC2H2SC2H2SC2H2C2H2SC2H2C2H2SC2H2C2H2SC2H2SC Ci: F, _S0oMC, Hi; II + (CH7) 7Cl6 13 2 36.3'3 c8f17so2nhc3h6h (ch3) “o3soc2h5 (cf3) 2cf (cf2) 6cooh.h2ïtc2h5 C7F C00H.H-UC H, r (CE, ) -c9k c00 “cy: lcomc3s6, h ^) 2 4 o 20 CgP so2j (c2h) oh2co2k c6Fi 3c2h4so2h (ch3) c 2ï / (ch3) 2c2h4coo-C ^ F. S0-IT (CH-CH0HCH ^ S03Na) C2HiN` (CH,) 0 O O p 2 2 2 5 30 p2

CgF1 702H4SCH (OH2COOïra) COOïTa C8I, i7C2HdSC2S4C0IIHC2H4iT + (CH3) 3C1 "25 C10F20HOC6H4S03'Ta (CF 3) 2 CF (CF 2) 4C0NÏÏC 2H4S03iIa ^" c6f1 3so2nhc2h6it + (CH 3) 2o2h4ohJ7oh "4fc6F13SO2N (CH2CH2OH) C3H6IT + (CH 3) 02E4OHj7oE 'c6f1 3so2 t (ch2ch2oh) c 3e6n (ce3) 2 and mixtures thereof.

The water-soluble fluorine-free surfactants used in the process of the invention are synthetic, non-perishable hydrocarbons-like organic compounds, which are water soluble at at least about 800 ° C at 25 ° C. 291-15 - 0.02 wt.% And are capable of promoting the film-forming ability of a usually non-film-forming aqueous solution of a fluorocarbon surfactant. Such surfactants accomplish essentially complete emulsification of at least one phase of a mixture of equal volumes of cyclohexane and water at a concentration of about 0.1-10% by weight of the water. In addition, the fluorine-free surfactants used according to the invention must be compatible with the fluoroaliphatic surfactants. Here, compatibility is understood to mean that no interaction occurs between the two types of surfactant to form an inactive product.

Fluorine-free surfactants particularly suitable for the process of the invention are those described in the aforementioned patents and they can be selected based on tests described in U.S. Pat. No. 3,772,195, Representative Fluorine -free surfactants suitable for use in the process of the invention include CgH ^ OSO ^ Va C10H21 ° S ° 5Sa

C1 2H25 ° S (Va 25 = 10H21S03K

a compound of the formula 1 C12H25IT (GH2CH2COOiTa) 2 C12H25rf + (CH3) 2 ° 2H4S03 30 CgH, 7020CE2CH (OOjCgH, 7) S0; aa c12h25h + (chJ301 (C8El70) 2P02ITa H0 (C2H40) a0 (C2H40) o , mole wt. 6500 ° 12H250 (C2H4 °) 4C2H40S05HEi 55 C8H17SC2H4C0ITHC (CH3) 2CH2S05: ia 800 32 91 - Η - C12H25S02N (CH2C0 ° ") c 3H6K + (CH35 3 C12H25i (CH3) 2 ° and mixtures thereof) It is known that certain fluorine-free silicone-based surfactants are suitable for forming AFFF solutions and these compounds can also be used here.

Generally, the weight ratio of fluorine-free surfactant to fluoroaliphatic surfactant is in the range of 1:25 to 10: 1.

The composition and nature of the shaped body or bodies may be such that, in addition to the two types of surfactants, they may also contain: various adjuvants, which assist in the processing or the composition of the shaped body (eg 15 solid polyethylene glycols or methoxy polyethylene glycols, with number average molecular weights of 1,000-20,000, preferably 1,000-6,000), foam stabilizers (eg, foam stabilizers based on polysaccharides), which stabilize the foam when administered to low alcohols, 20 ketones and others flammable polar liquids, and further adjuvants, which modify the softening temperature of the molded body (eg sorbitol), effervescent agents, which promote dissolution (eg citric acid with sodium hydrogen carbonate), adjuvants commonly used in the preparation of AFFF solutions (provided that these adjuvants are compatible with the one used too special combination of surfactants and the softening point of the desired shaped body not to drop prematurely below 50 ° C) and antioxidants and biocides, such as fungicides, which affect the stability and storage time of the shaped body or molded raise bodies. In some instances, individual fluoroaliphatic surfactants and fluorine-free surfactants may provide the desired AFFF solutions, but usually mixtures of two or more of each type of the surfactants are more readily available and can be applied to deliver more desirable AFFF solutions.

A particularly suitable composition for the shaped body is the following: C6F13SO2IT (CH2CH0HCH2SO;) CH2CH2CH2N'f '(CH3) 2CH2CH2O1 10-20 wt.% C8F1-SO3X'. 5-20 wt. ^ C ^ qH2 ^ OSQ ^ Ha 40-80 wt.

H0 (CH20H20) mH (average molecular weight 3,000-4,000) 0-20 gsvr.fo 10 H0CH2 (CH0ïi) 4CH20H (sorbitol) 0-20 wt.

Solid surfactant mixtures can be prepared by spraying an aqueous solution containing the fluororaliphatic surfactant and the fluorine-free surfactant (in the proportions described above) into a spray dryer, such as those manufactured is used by the ITiro Atomizer, Inc. and sold under the trademark "Iiro", which atomizer dryer has a diameter of 1.26 m. The atomizer dryer can operate with an air flow of about 7.5 m / min, with an air inlet temperature of about 80 ° C and an air outlet temperature of about 40 ° 0 is used. The solution can be dosed at a high speed (e.g.

24,000 rpm), a slotted disque disc rotating at the top of the unit sputtering the solution into very fine droplets. The droplets are dehydrated by the flowing air and the resulting solid particles are separated by an air cyclone separator. The particles can be in various ways, e.g. by extrusion, calendering, molding, and the like are formed into the required shaped body (s).

When the cartridge is a single-shaped body, this body is preferably in the form of a layer (which may be ribbed, profiled, etc. on one or both surfaces to increase the active surface), which is 800 3 2 91 - 16 - is rolled with a water-insoluble, water-permeable, open, resilient three-dimensional web, as shown in the drawing. A particularly suitable substrate for this purpose is the open, nonwoven, three-dimensional, low-density web, which is formed from a large number of intertwined, randomly arranged, flexible, durable, tough, organic fibers, placed in places where they meet cutting and in contact with each other by spheres of an organic binder, such as fibrous material, which are described in U.S. Pat. Nos. 2,958,593 and 5 "537" 121 are tightly bonded together, Commercially available products of such fibrous material with 70-95 $ empty space and made of thermoplastic fibers are sold under the trademark "Scotch-Brite", 15 bv Scotch-Brite type A, made from nylon 66 with a 12-15 denier (12-15 g / 9 * 000 m).

The single molded body may also be made by a water-permeable, water-insoluble reinforcing matrix, e.g. saturating a porous fibrous web, such as felt, wool wadding, etc., with a solution of the surfactant mixture and removing the solvent. The impregnated web or matrix can then be rolled up with a porous substrate, such as the aforementioned "Scotch-Brite".

The invention is further illustrated by the following examples, wherein the stated amounts are parts by weight and the water is deionized water unless otherwise indicated. For comparison of the described compositions, solutions in tap water were used, 50 with the concentrations of these solutions indicated in the tables. Where film coverage rates have been reported, these have been obtained by placing two drops of the AFFF solution on the surface of cyclohexane, which was at room temperature (approximately 22 ° C) in a 555 c® diameter Petri dish, and then time it took 800 3 2 91> «- 17 - the film to cover the surface.

Example I

The following ingredients listed in Table A were mixed together with stirring, then heated (85 ° C) for about 50 minutes to form a homogeneous solution.

TABLE A

5.88 parts CgP15S023T (CH2CHOHCH2SO ') CH2CH2CH2H + (CH5) 2CH2CI2OHa ·

2.95 caP17S03K

10 0.5 Ci2H250S05Na 11.4 C10H21OS05Na 22.1 Εθ (0Ε20Ή.2θ) ηΕ ** 22.1 CH30 (CH2CH20) nHC # 35 »0 water 15 a. Prepared according to the procedure described in Example 7 of Australian Patent 38028/72 by reaction of C6F13SO2U (ai) (CH2) 35r + (CH3) 2CH2CE20H with sodium 2-hydroxy-3-chloropropane sulfonate instead of propane sultone.

20 b. "Carbowax" polyethylene glycol 4000 (average molecular weight about 3000-3700).

c. "Carbowax" methoxy polyethylene glycol 2000 (average molecular weight about 19ΟΟ).

The hot solution (211 g) was used to saturate a piece of needle felt (65/35 polyester / viscose rayon, density 0.088 g / cm 3, thickness 0.32 cm) of 24 x U cm. The resulting impregnated felt was dried at about 100 ° C for 6 hours, most of the water being removed. The dried felt, containing the coalesced mixture, was cut to approximately 22 cm 30 x 14 cm and placed on a 15 cm x 24 cm x 0.5 cm piece of "Scotch-Erite" type A, after which the combined layers compactly rolled up with the "Scotch-Brite" textile on the outside, forming a 15 cm long and about 4 cm diameter pattern. The cartridge was fitted snugly in a galvanized steel pipe (4 cm 800 3 2 91 - 18 - x 5 c® length) threaded on both sides. Pipe caps with nipples for the hose were attached at each end The filled pipe or cartridge holder was inserted into the hose housing of a standard hand-held 5 portable water hrandhlusser of 9> 5 liters, the nozzle of which was replaced by an air-aspirating foam nozzle, the flow rate of which was "at 686 kPa about 20 liters / minute. The extinguisher was filled with approximately 9 5 liters of tap water and pressurized to approximately 686 kPa. The extinguisher was discharged to yield an APPP solution, which, as shown in Table B, is maintained during the discharge period. had a nearly invariable solute concentration, which was determined by refractive index measurements of samples taken at 1-5 second intervals,

TABLE · B

Time concentration of Film cover sec solute, velocity, _g / l_ sec_ 20 10 9 - 20 8 30 8 40 8 18 50 8 25 60 7 70 7 80 7 24

Example II

The ingredients listed in Table C were mixed together with stirring and heated (85 ° C) for about 30 minutes to obtain a homogeneous solution.

800 3 2 91 - 19 -

TABLE C

8.6 parts CgF., 3SO2I (CH2CH0HCH2SO4) CH2CH2CH2i + (CH5) 2CH2CH2OH

4.3 CqF17S05K

25.7 C1 () H210SO3! Ta 5 0.8 2H250S03Na 12.8 H0 (C12CH20) nHa * 12.8 H0CH2 (CH0H) 4CH20Hb * 35.0 water a. "Carbowax" 4000 10 b. Sorbitol

The aqueous solution (1,600 g) was spray-dried in a "! Tiro" spray dryer under the conditions described above, after which 1 wt.% Of vapor vapor formed silica ("fumed silica") (" Cabosil "MS-7) was added to obtain a free-flowing powder (8-65 micrometers).

A 150 g sample of the powdered product was pressed in a plate press at 6864 kilograms to form a coalesced solid flat layer having an average thickness of about 0.34 cm. This layer was cut to dimensions of about 13 cm x 19 cm, after which the weight was found to be 118 g. The layer was moved on a 15cm x 24cm "Scotch-Brite" type A web in the center of the narrow side, with one end (a) coinciding with the end of the web while placing a second 2.5 cm x 15 cm track over the compact layer at the end A to form a sandwich construction. After this construction was heated at 66 ° C for one hour to soften the solid layer, it was compactly rolled from -30 from the end A (with the larger piece of web on the outside) and into a 4 cm x 15 steel tube The tube was connected to a water fire extinguisher of 9> 5 liters, as described in example I. The extinguisher was filled with approximately 9.5 liters of tap water, which had been pressured to approximately 636 kPa with compressed nitrogen gas and 68 seconds 800 3 2 91 - 20 - fully discharged. A good quality AFFF solution of fairly equal concentration was obtained, as evidenced by the data set forth in Table D, obtained with samples taken during the discharge.

5 TABLE D

Time, Refractive Index Concentration Film coverage 20 sec n ^ dust dissolved rate, sec _sZi_ 10 2 1.3338 7 10 10 1.3338 7 9 '20 1.3337 8 11 30 1.3337 6 - 10 40 1.3337 8 15 15 50 1, 3337 6 15 80 1.3337 6 23 68 1.3339 8 6 tap water 1.3330 0 20 control 1.3339 8 6

The cartridge was removed from the holder and the web unrolled. The residual solid composition weighed 55 g, demonstrating that 63 g of the solid composition had dissolved, apparently evenly, resulting in an average concentration of 6.6 g / liter.

Example III

The ingredients listed in Table werden were mixed together with stirring and heated at about 80 ° C for about 30 minutes to form a homogeneous solution.

800 3 2 91 - 21 -

TABLE · S

parts 88.4 CgF15S022T (CH2CH0HCH2S0 ') CE2CH2CH2N + (CH *) 2CH2CH2OH 44,2 C8P17S03K 172 C10H210S05ïTa 5 7,5 c12H25os (yra 331.5 H0 (CH2CH20) nHa * 331.5 CH30 a CH2CH20,9 water). "4000 10 b." Carbowax ”2000

About 210 g of the above composition (a 65% solution) was poured into a 15 cm x 25 cm glass container over a 24 cm x 14 cm piece of needle felt (of the same type as in Example 1). The tray was placed in a pressurized air oven of 110 ° C, after which the water was evaporated in 6.5 hours from the "plastic" thus obtained. The solid plastic was turned over and in a vacuum oven 2 heated at 50 ° C for an hour, cut to 22 cm x 14 cm and placed on a 24 cm x 15 cm "Scotch-20 Brite" type A web, after which the combined layers were rolled up tightly with the web on the outside and then placed in a piece of steel tube of 15 cm, of which 4 cm was threaded. The tube was connected to a hose from a 9.5 liter water fire extinguisher, as described in Example II, after which the extinguisher was filled with approximately 9.5 liters of tap water and pressurized with nitrogen gas to approximately 686 kPa .

A layer of about 2.5 cm heptane (above a water layer) was lit in a square steel pan with a surface area of 4.65 m, then the heptane was left to burn for 30 seconds and then the fire in 71 seconds using extinguished substantially all of the contents of the fire extinguisher described above. Details of the associated conditions are shown in Table F.

800 3 2 91 - 22 -

TABLE F

Time, min + seo_Condition 0 '00 "ignition 5 0' 30" start of extinguishing fire 0 '40 "15 $ of the fire was extinguished 0' 50" 40 $. "" 0 »60" 90 $ "" 1 '10 "97 $" "10 1' 20" 99 $ "" 1 '30 "98 $" "1> 40" 99 $ "" 1' 41 "100 $" "10 * 56" attempt to re-light heptane with a torch, a small momentary flame was observed, but a fire could not be sustained.

When weighing the contents of the steel tube, after drying, it was found that 18 g of the solid material remained in the felt carrier and 110 g had been consumed in extinguishing the fire.

Example IV

A solution was prepared from the ingredients listed in Table G,

25 TABLE G

5.0 parts C6P1 ^ SO ^ CH ^ HOECEgSOpCH ^ E ^ HjïT ^ CE ^ CE ^ E ^ E

2.5 C8P17S03K

9.75 mixture (a) of 42 parts of C8H2 OSO2 Na and 57 parts of C10H210SO3Ua 0.4 Cl5E, OSO, iTa 24.5 E0 (CH2CH2O) nSVD; 24.5 CH30 (CE2CE20) nE ^ c) 33.35 water (a) Bit mixture is commercially available under the trade name "Stepan" 670-15 800 3 2 91 - 23 - (b) "Carbowax" 4000 ( c) "Carbowax" 2000

The pH of the solution was adjusted to 9.0 with 10% aqueous sodium hydroxide. The foam and surface activity properties, measured according to MIL specification F-24,385 B, Amendment 1, of May 16, 1969 in a solution containing 100 g of solid in 9 * 5 liters of water are shown in Table H.

TABLE 5 10 Foam expansion 25 $ drain surface interfacial tension (a) time (b), tension, between cyclohexane min micronewton / - and water micro-

at 22 ° C newtons / cm at 22 ° C

8.3 4.8 158 42 15 (a) ratio foam volume to solution volume.

(b) time to drain $ 25 of the liquid from the foam mass.

The above composition was applied to needle felt (of the same kind as mentioned in Example 1) in an amount such that after drying 0.39 S of coalesced solids were present per cm. A 10 cm x 25 cm piece of the dried impregnated textile product was placed on a 10 cm x 27 cm "Scotch-Brite" type A web and rolled and placed in a 4 by 10 ca tubular cartridge holder , as stated in example I. The cartridge holder was attached to a 9.5 liter water fire extinguisher, the extinguisher filled, pressurized and discharged as described in example I. During discharge, samples were taken and the concentration of dissolved dust and its film-forming properties, the results of which are reported in Table I.

800 3 2 91 - 24 -

TABLE I

Time, refractive concentration of film coverage sec index solute rate, 20 / __ 8/1 sec 5 12 1.3342 10 5 20 1.3341 9 5 30 1.3339 8 5 45 1.3339 8 5 60 1.3338 7 5 10 tap water 1.3330 0 control 1.3346 13 5

A fire test with 9> 5 liters of the control solution mentioned in the table, in which a fire extinguisher of 9 »5 liters 15 was discharged with an air-suction nozzle in 65 seconds, led to a control fire in 35 seconds and a total extinguishing in 63 seconds, Test fire was a 2 heptane fire with a surface area of 4 * 6 m, which was carried out according to the method described in Underwriters Laboratories Standard 711 20.

Example V

The ingredients listed in Table J were mixed with stirring and heated to about 30 ° C to form a homogeneous solution with a pH of 4.2.

25 TABLE J

divide 42.1 c.f_so „niozm + (ciIzzc: i" 013 2 5 ° ^. yy 21.05 c8? 17so2: ihc5h6u (ch3) 3ci · 8,3 c7? 15coo'H3: i + c3H6: ï + ( GE3) 2c2H4coo '30 145.8 H0 (C2H40) a (C3H60) b (C2H40) cHa * 70.9 H0 (CH2CH20) nHte 70.9 hoch2 (: how) 4ch2ohg * 5.9 ch3cooïi 3.55 CH ^ CONa 35 530.5 water s

X

v 800 3 2 91 * ts - 25 - а. "PLUROIC" F-77, molecular weight 6500 б. "Carbowax" 4000 c. Sorbitol

This solution (366.2 g) was used to saturate a piece of needle felt (of the same kind as described in Example I) in a glass container. The dimensions, drying treatments and cartridge manufacture were the same as described in Example III. The weight of the solid, coalesced mixture of surfactant compounds in the cartridge was 117> 5 g> that is 0.42 g / cm of the impregnated felt.

The cartridge was placed in a 9.5 liter water fire extinguisher, which was filled, pressurized and discharged as described in Example 1. During the discharge period, an AFFF solution was obtained with an effective and almost uniform concentration of solute, as determined by solute concentration measurements on samples taken at approximately 10 second intervals. The results are shown in Table K.

TABLE K

20 Time, refractive index concentration at 20 sec time solute, _dl- 2 1.3333 5 10 1.3333 5 25 20 1.3333 '3 30 1.3333 3 40 1.3333 3 50 1.3333 3 60 1.3333 3 30 70 1.3333 3 76 1.3335 4 tap water 1.3330 control 1.3339 8 800 3 2 91 - 26 -

Between the 2 and 10 second intervals, the foam expansion and the 25% drain time were measured, which were found to be 2.4 and 3.5 minutes, respectively. Analysis of the cartridge content at the end of the test showed that 25.2 g 5 of the 117.5 U of the solid material during discharge

was consumed. Calculations showed that 2.7 g of solute / liter must have been present in the discharged solution, which value is very close to the obtained value. As long as the AFFF solution was very dilute, it was suitable to delay evaporation of the volatile solvents. Example VI

The ingredients listed in Table L were mixed together with stirring and heating.

TABLE · L

11.2 parts of CQF1

22.4 C6F15S02li (CH2CH0HCH2S0 ") C12CH2CH2lT + (CH5) 2CH2CH20H

350.3 sodium alkyl sulfates ("Polystep" B-25, a 38.65¾ aqueous solution of CgH 2 OSO 2 Na, C 2 H 2 OSOjEa and C 2H 2 ^ 0SO 2 Na in a weight ratio of about 2:75 * 23 ) «

The water was evaporated to yield 305.3 S solution. About 2 µg of this was poured into a 15 cm x 25 cm glass vessel containing a 24 cm x 14 cm piece of needle felt (of the same type as mentioned in Example 1). The tray and its contents were heated at 108 ° C for 13 hours, removing substantially all of the residual water (within 2 g of the expected dry weight, which is about 1.5% water content). felt was pressed in a plate press at 25 ° 0, cut to 13 cm x 19 cm, placed on a 15 cm x 24 cm piece of nonwoven fabric and heated to soften the coalesced solids, after which the combined material was coiled and placed in a 4 cm x 15 cm steel tube, which was threaded and equipped with nipples for connection to a hose, 800 32 91 ff - 27 -

The resulting cartridge was connected to a standard 9 liter 5 liter fire extinguisher, the extinguisher filled with approximately 9> 5 liters of tap water, pressurized to 686 kPa and fully discharged in 64 seconds. An effective AFFF solution with a fairly uniform composition was obtained, as evidenced by the data listed in Table M, obtained from samples taken during the discharge.

TABLE M

10 time,. refractive concentric film surface boundary seo index tration cover tension, tension 20 n ^ to opacity micronewton / - between release rate cm at 22 ° C cyclohexane dust, water, 15 g / l sec micronewton / - crn at 22 ° 0 2 1, 3341. 10 60 (a) 176 40 .10 1, 3337 6 60 (b) 20 1.3336 5 21 180 33 20 30 1.3337 6 45 40 1.3336 5 14 180 33 50 1.3336 5 18 60 1.3336 5 55 180 32 64 1.3337 6 35 25 control 1.3339 8 8 176 42 tap water 1.3330 0 - (a) 25 $ of the cyclohexane surface covered in 60 sec (b) 90 $ of the cyclohexane surface covered in 60 sec.

30 Example 711

The following solid ingredients were sieved separately and then mixed together 11.3 g of V17so3x 22.7 S 06P13S02i (OH2CHOECE2SOj) OE2OH2S2: i + (CH5) 2aH2OH2OH 35 135.0 g of sodium alkyl sulfates ("Polystep" 3-25, dried 800 3 2 91-28 solids).

The mixture was heated to 100 ° C and several times on a plate press. pressed, obtaining a solid, light yellow brown-colored, waxy coalesced layer with an average thickness of 0.34 cm, After cutting, the dimensions of the compact layer were 13 cm x 19 cm, while the weight was 114 »5 8. The layer was softened by heating at 110 ° C, placed on a 15 cm x 24 cm "Scotch-Erite" type A web, after which the combined layers were rolled up and placed in the previously described assembled tube, The cartridge thus prepared was connected to a standard 9.5 liter water fire extinguisher, the extinguisher filled with 9.5 liters of tap water, pressurized to 686 kPa and fully discharged in 57 seconds. As shown in the data shown on samples taken during discharge, an effective AFFF solution of very uniform composition was obtained.

TABS! H

time, refractive concentric- film- surface-interface-20 sec index tration covering tension, tension n ^ at calibration micronewton / - between discharged speed cm at 22 ° C cyclohexane dust, unit, and water, g / l sec micronewton / -

25 _____________cm at 22 ° C

2 1.3338 8 11 10 1.3338 8 17 164 35 20 1.3338 S 16 30 1.3337 7 12 165 34 30 40 1.5337 7 10 50 1.3337 7 9 167 34 '57 1.3339 8 11 control 1.3339 8 5 162 39 tap water 1.3330 0 800 3 2 91 i? -29--

The weight of the compact layer of coalesced solids that remained after discharge was 53 * 3 g * showing that 61.2 g had dissolved, which corresponds to an average concentration of 6.5 g of solute / liter.

5 Example VIII

From. the powdered surfactant product described in Example II was mixed 190 g with 19 g of a powdered polysaccharide gum (K 8 A13, prepared by Xelco Division of Merck & Co.) and the resulting mixture pressed in a plate press at 6864 kPa to form a coalesced compact flat layer. Two layers with a thickness of 0.25 cm were prepared and cut to the dimensions 13 * 3 cm x 14 * 0 cm (weight 128 g). Using a sawtooth pattern shape (with troughs with a depth of 0.18 cm and a distance between peaks of 0.35 cm), both surfaces of the layers were at right angles to the longest dimension grooves pressed. These layers were placed end to end with the shortest dimensions adjacent to each other on a piece of "Scotch-Erite" textile 20, then heated until they softened and the resulting construction was at right angles to the direction of the grooves rolled up in the layers to form a pattern as described in Example II. The cartridge was placed in a polyvinyl chloride plastic tube with the following dimensions: length 15> 2 cm, outside diameter 4.48 cm, inside diameter 4.25 cm. This mount was placed in a cartridge holder-nozzle assembly made of acrylic nitrile / butadiene / styrene (AES) plastic as shown in Fig. 2 (the cartridge holder had a 15 * 2 cm long cavity and an inner diameter of 4.50 cm ). This assembly was connected to a 9 * 5 liter hand portable water fire extinguisher, the extinguisher was filled with about 9 * 5 liters of tap water at 21 ° C, pressurized with nitrogen to 686 kPa and at 66.5 fully discharge for seconds.

800 3 2 91 - 30 -

Foam samples were taken during the discharge intervals listed in Table 0 and a number of properties of these samples were measured which are summarized in this Table.

TABLE 0 5 time, breconcentre- foam- 25 $ Upper-Limit-film-sec- tion expansion expan- sion-surface-area-deck-index at option time, span- 20. ,.

n ^ discharged min nmg, mng, quick dust, micro micro, 10 g / l newton / - newton / - sec cm at cm at _22 ° C 22 ° C_ 5 1,337 6.1 · 8.6 5, 3 168 33 8 40 1.33355 4.8 7.8. 2.2 168 33 13 15 control 1.3338 7.0 - - 167 33 3.5 piping water 20 1.3330 - -

The weight of the remaining compact coalesced layers in the cartridge holder was J1 g, demonstrating that 57 g had dissolved (44 ^ ·)

In another example, similar to that described above (except that the polysaccharide was dried to remove accidental moisture, and that the ratio of the powdered surfactant product to the dried polysaccharide was 188 g: 12 g ), dissolved a larger percentage of the solid mixture: 74 g of 30 out of 128 g (58 ^).

Example IX

The ingredients listed in Table P were mixed together under stirring and heating to about 85 ° C for about 30 minutes to obtain a homogeneous solution.

800 32 91 - 31 -

TABLE F

share 7.9 cgP1 5so2n (gh2chohch2so ") ch2ch2ch2h + (ch3) 2ch2.ch2oh

4.0 ° CaPt7SO3K

5 23,4a * C10H210S03Na0,6a * C. -Hj-OSO ^ yJa0,7 55 5 Λ 12 H0 (CH2CH2O) aH * 12 HO (CH2 (CHOH) 4CI2OHe * 0,06 ortho-phenyl sodium phenolate, 4H20 ^ * 10 0.06 para-methoxyphenol 40 water a. Solid based b. "Richonol" 7227 c * "Fiaproof" Anionic 7 15 4 · "Carbowax" 4000

e. Sorbitol -f. "Dowicide" A

The aqueous solution (about 10 kg) was spray-dried in a "Firo" spray dryer under the conditions described above, after which about 1 wt. Of vapor formed "fumed" silica ("Cabosil" MS-7) was added, whereby a free-flowing powder with a residual water content of about 1 ^ was obtained. Approximately 2.3 kg of this powder was pelleted at ambient temperature in a California Pellet Mill, model CL, using a nozzle with a diameter of 0.48 cm to obtain small cylindrical pills of the following dimensions : diameter about 0.46 cm, length 0.53-0.9 cm (average about 0.6 cm) and a density of 1.28 g / ml.

120 g of the pellets (with a total active surface of about 1150 cm) were placed in a phenolic resin impregnated cardboard sleeve (outer diameter 4.48 cm, inner diameter 4.25 cm, length 15.2 cm). In order to retain the pills in the sleeve as an aggregate, each end of 800 3 2 91 - 32 - the sleeve was fitted with a disc of "Scotch-Brite" textile, the diameter of which was 4 »3 cm and wherein the external surface of the disk was located about 0.5 ca from the sleeve end, while a drop of RTV silicone rubber was used to seal each disk at its connection to the sleeve.

The filled sleeve was inserted into the sleeve holder nozzle assembly of Example VIII (Figure 2) and connected to a 9 liter 5 liter hand-held water fire extinguisher.

The extinguisher was filled with about 9 ♦ 5 liters of tap water at 21 ° C, pressurized with nitrogen gas at about 686 kPa and discharged in 61 seconds.

As can be seen from the data of Table Q obtained from foam samples taken intermittently during the discharge, a good quality AFFF solution and a fairly uniform concentration was obtained.

TABLE Q.

time, refractive index concentration of film overlay 20 sec n ^ solute, rate, 20 µg / liter_sec 2 1.3348 14.4. 1.5 10 1.3346 12.8 1.5 20 1.3345 10.4 2 30 1.3340 8.0 3 25 40 1.3338 6.4 6 50 1.3338 6.4 4 60 1.3338 6.4 5 tap water 1.3530 0 30 control 1.3340 8.0 4 ITa discharge, the cartridge was removed and the remaining pills dried in an oven with circulating air at 110 ° C for 6 hours. The weight of the dried solids was 20.7 g, which shows that 99.3 g had dissolved.

35 800 32 91 f A- • 33 -

Example X.

The ingredients listed in Table E were powdered separately and mixed together.

R1 R

5 13.3 parts 5S02li (C12CH0HCH2S0 ") CH2CH2CH2IT + (CH5) CH2CH20H

6.7 C8F17S03K

80 sodium alkyl sulfates a * a. Solids obtained by evaporation of the water from "Polystep" B-25 Using a. Small laboratory plastic extruder, the mixture of powder surfactants listed in Table R was pressurized in the form of a continuous rod under heating (56-75 ° C) and pressure. The light yellow-brown colored bar (diameter 0.39 cm, density 1.41 g / ml) was cut into pieces about 12.7 cm long, while 81 of these bars (total weight 172.3 g, total active surface about 1275 cm) as an aggregate were placed in a cardboard cartridge case of the same type and dimensions as described in Example IX. Caps were applied to the ends of the filled sleeve using discs made of "Scotch-Brite" textile, while these ends were sealed with RTV silicone adhesive, as described in Example IX.

The filled sleeve was inserted into the cartridge holder-mouthpiece assembly of Example 7III and connected to a 9.5 liter hand-portable water fire extinguisher. The extinguisher was filled with approximately 9.5 liters of tap water, pressurized to 686 kPa with nitrogen and completely discharged in 5 seconds for 5 seconds. As can be seen from the data listed in Table S, which were obtained with foam samples taken intermittently during the discharge, an effective AFFF solution with a very uniform composition was obtained, 800 32 91 - 34 -

TABLE S

time, refractive index, film coverage concentration 20 sec n ^ Solute, velocity, _ g / liter_sec_ 5 2 1.3334 3.2 24

10 1.3335 4.0 U

20 1.3335 4.0 12 30 1.3335 4.0 12 40 1.3335 4.0 13 10 50 1.3335 4.0 Θ tap water 1.3330 0 control 1.3340 8.0 7

The weight of the undissolved bars of the cartridge 15 was (after drying) 127.3 g, which shows that 45.0 g of the solid had dissolved.

Example XI

After drying in a vacuum oven (T5 ° C, 18 hours), 557 g of the powdered product of surfactants mentioned in Example 2 and 45.9 g of powdered polysaccharide gum (K8A13) were mixed intensively. The bit mixture was bar-shaped using a small laboratory extruder at a cylinder temperature of about 50 ° C and a nozzle temperature of about 65 ° C. The light yellow-brown colored bar (diameter 0.38 cm, density about 1.38 g / ml) was cut into pieces about 1.5 cm long, after which 120 g of these pieces of bar (with a total active surface (about 1050 cm) placed as an aggregate in a sleeve of the same type and dimensions as described in Example IX. The ends of the filled sleeve were capped in the manner described in Example IX with "Scotch-3rite" textile disks and sealed. The filled sleeve was inserted into the cartridge holder nozzle assembly of Example 7III and connected 800 32 91 - 35 with a 9 5 liter hand portable water fire extinguisher. The extinguisher was filled with approximately 9.5 liters of tap water (21 ° C), pressurized to 686 kPa with nitrogen and fully discharged in 68 seconds. As can be seen from the data reported in Table 5, which were obtained using foam samples taken intermittently during the discharge, it appears that an effective APPF solution of very uniform composition and properties was obtained.

10 TABLE · T

time, refractive index concentration of film coverage 20 sec Hg solute, velocity, _ g / liter_sec_ 2 1.5538 6.4 8 15 10 1.3538 6.4 7 20 1.33375 6.0 10 30 1.3337 5, 6 12 40 1.3337 5.6 12 50 1.3337 5.6 11 20 60 1.3337 5.6 13 pipe 3 water 1.3330 0 control 1.3340 8.0 3

The weight of the undissolved pills of the cartridge 25 was 57.7 g (after drying), which shows that 62.3 g had dissolved.

800 32 91

Claims (12)

1. A hand-held fire extinguisher with a tank, which may contain pressurized water, a valve mounted on the tank, a hose connected to that valve and an air suction nozzle connected to that hose, characterized in that a cartridge holder is inserted into the tubing and connected to the mouthpiece, this container being filled with a cartridge containing a molded body consisting of a solid, coalesced mixture of a water-soluble fluorine-containing aliphatic surfactant and a water-soluble fluorine-free surfactant compound, and of the molded body at least one exposed surface is adapted to be contacted with water flowing through the cartridge holder, dissolving the molded body and during the period of discharge of the water from the tank forms an aqueous film-forming foam solution of a relatively constant composition. 2. Fire extinguisher according to claim 1, characterized in that the cartridge is a single-shaped body containing the mixture of surfactants. Fire extinguisher according to claim 1, characterized in that the cartridge consists of more than one of said shaped bodies in the form of a water-permeable aggregate. 4. Fire extinguisher according to any one of claims 1-3, characterized in that the exposed surface is adjacent to a water-insoluble, water-permeable medium, so that the cartridge is provided with at least one channel, through which the water comes into contact with said surface can flow. 5. Fire extinguisher according to any one of claims 1-4, characterized in that the cartridge consists of an intermediate product, containing two types of layers in the form of a roll, one of the layer types containing said solid mixture and the other layer type consists of a water-insoluble, water-permeable, open, resilient and three-dimensional web, 800 32 91 - 37 - 6. Fire extinguisher according to any one of the preceding claims, characterized in that the shaped body consists of a composition of said solid mixture, which is distributed through a water-insoluble, water-permeable reinforcing matrix. Fire extinguisher according to one of the preceding claims, characterized in that the fluoroaliphatic, surface active compound corresponds to the formulas (Hf) a (5) nZ, 10 in which a fluorinated, saturated, monovalent organic residue having the end group a perfluoromethyl group, which contains 3-20 carbon atoms and of which the carbon atoms of the chain only contain fluorine, chlorine or hydrogen atoms, wherein for every 2 carbon atoms there is no more than 1 hydrogen-15 or chlorine atom and in which a divalent chain is present in a skeletal chain oxygen atom or trivalent nitrogen atom, which is bound only to carbon atoms, may be present, n = 1 or 2, 20. represents a polyvalent linking group, m is an integer from 0 to 2, and Z is a water-solubilizing polar group and wherein said fluorine-free surfactant is a synthetic, non-perishable hydrocarbon-like organic fluorine-free compound is a surfactant which is water soluble at 25 ° C to at least about 0.02 wt% and which is substantially at least one phase of a mixture of equal volumes of cyclohexane and water at a concentration of about 0.1 to about 30 wt.% of the water fully emulsifies, the weight ratio of the fluoroaliphatic surfactant to the fluorine-free surfactant in the body being from 10: 1 to 1:25. 8. Fire extinguisher according to any one of the preceding claims, not characterized in that said solid mixture further contains solid polyethylene glycol or methoxy polyethylene glycol having a number average molecular weight of about 1000 to 20,000 under normal conditions. A method for extinguishing Class A 5 or Class S fires, using a foam of an aqueous film-forming foam solution of relatively constant composition of a water-soluble fluororaliphatic surfactant and a water-soluble fluorine-free surfactant, with characterized in that the foam solution is obtained by flowing a predetermined amount of water under pressure in contact with the surface of at least one shaped body, which consists of a solid, coalesced mixture of said surfactants. 10. A molded body, characterized in that it contains a solid, coalesced mixture of a water-soluble fluororaliphatic surfactant and a water-soluble fluorine-free surfactant, which has at least one exposed surface in the molded body. that upon contact with a predetermined amount of flowing water is dissolved to form an aqueous film-forming foam solution of relatively constant composition. 11. A water-permeable aggregate of more than one shaped bodies with an exposed active surface, characterized in that each of said bodies is a solid, coalesced mixture of a water-soluble fluororaliphatic surfactant and a water-soluble fluorine free surfactant, said aggre-50 has a predetermined active surface which, when contacted with a predetermined amount of water flowing at a predetermined rate, is dissolved to form an aqueous film-forming foam solution of relatively constant composition . 12. A mixture of a water-soluble, fluororaliphatic surfactant and a water-soluble, fluorine-free surfactant, characterized in that the mixture is a solid, coalesced mixture of said surfactants, wherein the mixture dissolves on contact with a stream of a predetermined amount of water flowing at a given rate to form an aqueous film-forming foam solution of relatively constant composition. 800 32 91 Ml? CH2 CaH. J- | ^ iJ2CH2OCH2COONa 0 17 ^ CH ^ COONa OH 2 Minnesota Minin-7 and "ani ^ aotr · - · -" --.pany 800 32 91