United States Patent 1 ‘Schuierer et al, ro] 4,209,407 (45) Jun, 24, 1980 [54] FIRE EXTINGUISHING AGENT {75} Inventors: Erich Schuierer, Burghausen; Heinrich Bathel, AltStting; Richard Brill, Langen, all of Fed. Rep. of Germany [73] Assignee: Hoechst Aktiengeselischaft, Frankfurt am Main, Fed. Rep. of Germany [21] Appl. No.: 890,203, [22] Filed: Mar. 27, 1978 [30] Foreign Application Priority Data Mar, 30,1977 [DE] Fed. Rep. of Germany... 2714013 [51] Int. a2 .. AGI 1/00; A62C 1/12 [2] Us. snes 252/34 169/47; 252/8.05 [58] Field of Search... 52/3, 8.05; 169/47 56) References Cited US. PATENT DOCUMENTS 3,856,535 12/1974 Ferguson 252/81 4099,574 7/1978 Cooper etal. vas 252/3 Primary Examiner—Leland A. Sebastian Attorney, Agent, or Firm—Connolly and Hutz bn ABSTRACT New aqueous concentrates containing a fluorinated surfactant and a further foam producing component are disclosed. They contain of from 0.5 to 2.5% by weight a fluorinated phosphorous acid ester having the formula Be fT © R(CP=CH yg (CHty-H—Q-O- B08 In this formula means Rya perfluoroalkyl radical with from 3 to 16 carbon atoms, m zero oF I, pan integer of from 1 to 4, Ria hydrogen atom, a C1.salkyl radical, a eyleohexy! radical or a 2-hydroxyalkyl radical with from 2 to 6 carbon atoms, Ro a C14 alkyl radical, a cyclohexyl radical or a2-hydronyallyl radical with 20 6 carbon atoms, or a radical of the formula Ry-—(CF-=CH)n—(CHa)p Q an alkylene radical with 2 104 carbon atoms, which may be substituted by phenyl groups. The aqueous concentrate when diluted with about 16 parts by volume of water gives a solution ‘hich can be foamed. The foam it capable of extin- guishing liquid hydrocarbon fires. 15 Clsims, No Drawings4,209,407 1 FIRE EXTINGUISHING AGENT The present invention relates to fire extinguishing agents, which confainas the main constituent a surface: $ active fluorine compound. Surface-actve fluorine com- pounds have been used in recent years in fire protection. ‘Their particular importance resides in the fact that they disperse on non-polar combustible liquids in the pres- ence of water to form an aqueous film which covers the 10 whole surface end, toa certain degree, provides a pro- tection against reignition. Tt has been ascertained that frequently a concentra- tion ofa fuorinated surfactant of about 0.1% by weight, calculated on the aqueous solution to be foamed, suf- fices to extinguish hydrocarbon fires and that the sur- face tension of this solution should be below 20 dyn/cm, if possible. Fluorinated surfactants are relatively expensive. Tt was, consequently, a tsk to develop a cheap fluorinated surfactant which fulfils the above requirements when used in practice. Tthas now been found that phosphorous acd esters of, the formula 25 hie © BCPC a ICH N—O-P=O8 RO 30 are excellently suitable as constituent of foam fire extinguishing agents. In the above formula Ryis a perfluoroalkyl radical with from 3 to 16 carbon atoms, mis Oor I, pis an integer of from 1 to 4, Ri is a hydrogen atom, a C1. alkyl radical, a cyclo- hexyl radical or a 2-hydroxyalkyl radical with from 2to 6 carbon atoms, Rais a Ci. alkyl radical, a cyclohexyl radical, a 2- hydroxyalkyl radical with from 2 to 6 carbon atoms, oF a radical of the formula Ry—(CF=CH) (CHa), Q is an alkylene radical with from 2 to 4 carbon atoms, which may be substituted by phenyl groups. This is applicable, for example to foam extinguishing agents, in which the foam producing component is pro- tein hydrolysate or a synthetic imputrescible organic surfactant. In both cases, additions of the fuorine com- ponent Iin small amounts improve the extinction effect. ‘Advantageously component I is employed together with a second foam producing fluorinated surfactant component. Among appropriate second components, cation active surfactants may be mentioned, especially, however, non ionie surfactants containing a perfluoro- alkyl group. Excellently suitable are in particular non ionic fluo- rine-containing amides of the formula TI 35 0 45 55 F(CF CONHI(CHSNCHCH:OH 2 a, in which ais an integer of from 6 to 10 Fluorine-containing amides of this type are known from German Auslegeschrift No. 21 27232. ‘The present foam concentrates have the advantage that a fluorinated surfactant II which considerably re- duces the surface tension is combined with a fluorinated surfactant I which has a rather high surface tension but ‘Which can be obtained in cheap manner. Thus, there is ‘6 2 obtained a cheap and appropriate water film-forming foaming agent. Suitable compounds of the formula I are especially compounds of the formula Ia ee Ry/CPCHCHy“HO—Q-0-F-08 Ri ° a jin which Ry is an alkyl radical with from 1 to 4 carbon atoms, a7-hydroxyalkyl radical with from | to 4 carbon ‘atoms or a hydrogen atom. Especially preferred are compounds of the formula Ib chy gh at CF eMCERCH— CH BRC E CHO F 08 RCH thas moreover been found that, instead of the phos- phorus-containing esters I compounds of the formula II free from phosphorus " B(CP=CHg (Chip BH—I—OH AS R au in which Ry m, p, Ri, Reand Q are defined asin formula T and AG is @ water-solubilizing anion, may be used together with the compounds of the formula TI as addi- tives to foam-type fire-fighting agents. The anion AG is not critical. For example anions such as nitrate, sulfate, acetate or halide, especially methosulfate, may alternatively be used. Especially suitable for this purpose are those repre sentatives of the formula IIT which have the formula amy Inthe formula III Q and A@ have the same meaning as in the formula TH, Ry i an alkyl radical with from 1 t0 4 carbon atoms, preferably 1 to 2 carbon atoms, espe- cially the methyl radical. Suitable anions A@ are for example halides, for example a bromide or iodine, or rmethosulfate or an acetate The weight ratio between II and Ill or between II and Ia is at most 1, but is preferably in the range of from 0.5 to 0.05, in particular of from 03 to 0.1. The absolute quantity of fluorinated surfactant in the foam concentrate (prior to adding the extinguishing water) is in the range of from about 05 to 2.5, preferably of from 1 t0 2% by weight. These relations may also be applied to the system II/. Suitably the radical Ryin the compounds I and IIL has of from 5 to 12 carbon atoms. Advantageously Q is CHL or ota enm. on4,209,407 3 Preferably the product (mp) is zero of 1 ‘The foam concentrate may contain, in addition to fluorinated surfactants, water and the foam-producing. component (synthetic surfactant or protein hydroly- sate) further known additives, for example antifreezing 5 agents, corrosion inhibitors and foam improving agents. Suitable foam-improving agents are, for example, alkyl glycols such as monoalkylethyllene glycol having C14 aklyl. The portion of these alkylglycols in the foam concentrate may amount up to 35% by weight and is preferably in the range of from 20 to 30% by weight. For extinguishing purposes, the foam concentrate is diluted with water and thereafter foamed. The dilution is effected with water for example in a 10- to 20-fold ‘quantity of the foam concentrate. The solution entering the foam tube, consequently, contains of from about 91 to 97% by weight of water. The solution also contains from 0.01 to 1%, especially 0.03 to 0.3% of the fluori- nated surfactant of formula I. ‘The foam production may be carried out in usual manner, by injecting air (or an other noncombustible 283). The compounds of the formula IIT are known, for example from U.S. Pat. Nos. 3,257,407; 3,535,381; Ger- ‘man Offenlegungsschriften 22 44 297; 21 41 542 and 17 668 939 and may thus be prepared according to known processes, Especially suitable for the admixture with com- pounds of the formula IT are those compounds of the formula TIT in which at least one of the radicals Ry and Rz is a 2-hydroxyalkyl radical having of from 1 to 4 1s 2» 25 carbon atoms. The compounds of the formula I may be 2° ‘obtained from amines of the formula RACFCHar(CHD NR by reaction with eyclic phosphites of the formula 35 0 ow NS, of Su 0 at a temperature of from +20" to +140" C. The rese- tion is preferably carried out in the presence of polar solvents, Said reaction is preferably carried out at a tempera- ture of from +20" to +140" C,, preferably of from +60" to +140" C., suitably while frst placing the fluo- rine-containing amine heated to the resction tempera- ture into the reaction vessel and slowly adding the eye- lic phosphorous acid ester serving. as the alkylation lar weight ratio habe been set up. is advisable to superpose the reaction mixture with an inert gas, for example nitrogen. The reaction is preferably carried out at atmospheric pres- sure, but may likewise be performed under reduced pressure, or especially suitably in the presence of sol- vents, under a slightly elevated pressure. The reaction requires on principle no solvent. However, for a better handling of the starting and final products, which ate highly viscous at room tem- perature, polar solvents are suitably used which advan- tageously should be capable of dissolving both the start- ing and the final products. Especially appropriate are polar solvents, for example methanol, ethanol, sopropa- nol, methylene chloride, chloroform, glycol and dime- thyiglycol. At the generally employed reaction temper- atures of fiom +60" to +120" C,, the reaction ends after about 2to 4 hours. However, it has proved advan- 4 35 4 tageous to add during the reaction process a small quan- tity of water, preferably of from 1 to 10 mol %, in order to improve the conversion and the reaction velocity. Further details concerning the preparation of the phosphorous acid esters I may be found in copending application Ser. No. 859,051 filed Dec. 9, 1977, now US. Pat. No. 4,147,743. The invention will be illus- trated by the following examples: EXAMPLES The tests were on principle carried out using the following standard test method: A circular fire basin (diameter 1.9 m; area of fire 2.83, 1m; height of the basin 20 cm) was filled each time with 150 liters of jet propellant JP 4. After the propellant had ‘been set on fire and burned for a period of 2 minutes, the aqueous foamable solution containing the fluorinated surfactant with a content of foam concentrate of 6% by volume was directly sprayed on to the fire by means of « laborator-type foam jet tube, at a rate of 10 liters/mi- nute of water flow, at an angle of inclination of 45° C. ‘The foaming number (ratio between volume of the foam and volume of the used liquid) was about 7 to 8. The following foam concentrates were examined and the extinction time was determined: EXAMPLE 1 (029% by weight of Noorine containing eraciamt CyrisCONH(CIT N(CH CHOM2 13% by weigh of Moore containing surfactant HOH CHs —H CoP UCP CCH BCH ECHO —O8 cH cH 100% by weight of Cz. alkyslfate as effective foaming agent, ethanolamine sal, 250% by weight of ethylene glycol as antifecsng agent 250% by weight of buy! glycol as antifeering agent, 383% by welght of water 100.0% by weight of fing concentate tinction time: seconds EXAMPLE 2 (029% by weigh of fluorine containing sfacont CyF sCONH(CH:)N(CH{CH:OM by weight offuorine-contaning surfactant (Gi sCPSCH— CH= ON(CH)2C HOH)SO{CH®) by weight of alkysulfate of Example 1 250% by weight of butyglycol as antifreezing agent 250% by weight of etylene peo! as anifesring agent 38356 by weight of water 100% by weight of foam concentrate tinction time 60 seconds 16 1005 EXAMPLE 3 (029% by weigh of acre containing svfactant (CyFisCONH(CH)N(CHCH;OH)2 1.3% by weight of fuorine-conaining srfactant (GrF sCF=CH—CHy—EN(CHY:CH.OH) CIO 10.0% by weigh of alkyelate of Example 1 250% by weight of batylplycol se atifeesing agent 250% by weight of ethylene pleol as antifeesng agent 383% by weight of water 100% by weight of fem concentrate4,209,407 -continued ‘Sinton Une: 50 seconde EXAMPLE 4 1.5% by weight ofthe phosphoravcontaiing Roornated sfactant of Example | 100% by weight of alkymlate of Example 1 2505 by weight of buylgycol ss antifessing agent 250% by weight of ethylene glycol as atieezing agent 3830 by weight of water 100.0% by weight of fom concentrate ceninction Une afer 90 second, contol ofthe fe, but no complete 10 1s EXAMPLE 5 Example 4 was repeated under modified test condi- tions. There was used a circular concrete fire basin of a surface of 10 min which the height of the water was 5 com. The nature and the quantity of the combustion substances corresponded to those of Example 1. The oil layer in the trough was about 3 cm thick. 2 period of burn: 15 seconds foam jet tube: 25 liter/min. of water flow, direct appli cation of the foam. Additive: 5% by volume to the extinction water. ‘Average extinction time: 3 minutes, 44 seconds. EXAMPLE 6 The foam concentrate of Example 1 was examined under the conditions of Example 5. 3 Average extinction time: 2 minutes, 24 seconds. EXAMPLE 7 The following composition was tested under the con- ditions of Example 1: 0 Ti by weight of fisornated saan CrFisCONH(CH)N(CH;CHOH2 100% by weight of alkyslat of Example 1 250% by weight of buyp}ycol as antifecting agent 250% by weight of ethylene glycol as antiecang agent $96 by weight of water 100.0% by weight of foam concentate —CH;—. 10, Foam concentrate as claimed in claim 9, wherein a phosphorous acid ester of the formula 1s Bo gt 8 CPCH CH) BN—CHy— ECHO“ P08 oh oh is used, 111, Foam concentrate as claimed in claim 1, contain- ing from 0 up to 35% by weight of a monoalkyl ethyl- ene glycol, 12. Process for the extinction of a burning liquid hydrocarbon by covering the area of fire with a foam consisting of a non combustible gaseous phase and an aqueous liquid phase, wherein the liquid phase contains of from 0.01 to 1% by weight of an ester of claim 1 13, Process as claimed in claim 12, wherein the con- tent of said ester is in the range of from 0.03 to 0.3% by weight. 2s 35 4 50 35 8 14, Foam concentrate for fire- taining water, at least one foam producing fluorinated surfactant and a further foam producing component which comprises an ionic fluorine-containing com- pound of the formula R t RACF=CHg (Cty PN—G—OH AS RB in which Ryisa perfluoroalkyl radical with from 3 to 16 carbon, atoms, mis zer0 or 1, pis an integer of from 1 to 4, Ry is a hydrogen atom, a C1. alkyl radical, a cyclo- hexyl radical or a 2-hydroxyalkyl radical with from 2 to 6 carbom atoms, Ra is a Ci. aklyl radical, a cyclohexyl radical or a 2-hydroxyalkyl radical with 2to 6 cerbon atoms, or a radical of the formula R-—(CF-=CH)y—(CH2)p, is an alkylene radical with 2 to 4 carbon atoms which may be substituted by phenyl groups, or the radical —CH2—C(CHs)—CHa—, and AG is a water-solubilizing anion, and non-ionic fluo- inated compound of the formula (CF) CONHI(CH2)N(CH:CH;OH)z in which a is an integer of from 6 to 10. 15. Concentrate as claimed in claim 14, wherein the weight ratio of non-ionic fluorinated compound to ionic Aluorine-containing compound is smaller than I or equal to 1 and the absolute quantity of fluorinated surfactant is in the range of from 0.5 to 2.5% by weight.