‘US 2006009135081 cu») United States 2) Patent Application Publication co) Pub. No.: US 2006/0091350 A1 Clark (43) Pub. Date: May 4, 2006 (Si) USE OF FLUORINE-FREE FIRE FIGHTING Publication Casieaton AGENTS (76) tnveor Kitna P. Clark, Mansi TX (US) G1) Inte 4e2D" 100 200601) Conesponience Ads @) ta 2a GRADY K. BERGEN S353 PEE PARKWAY SUITE aoa ‘ DALLAS TX 78219 US on austeact cy es A foam concentrate proves fresighing composition ‘thor mised wisest he e-Ang eompoton eye ae thes ut frm a suble seal on ecloeuane ses UL 162, Class 8 perormanc eed fora ast one of PPP Related U.S. Application Data as att faooprotain TP) agen witout ogerng ergmieMnvie The comet fered om wae and (©) Divisio of eppiation No. 106003810 fied on Jun. a hgh mefectlar Weight acc polmer CAMIWAP) at 20, 2003, now Pat. No, 7,005,082, ‘oonlinating satUS 2006/0091350 AI USE OF FLUORINE-FREE FIRE FIGHTING "AGENTS, [0001] This eppication is division US. patent applica tion Ser. No. 10/600,810, filed Jun. 20, 2008, entitled “Pluorine-Free Fite Fighting Agents aad Methods, ‘TECHNICAL FIELD. [0002] The invention relates generally to fire-fighting ‘agents. BACKGROUND [0003] Aquoous film forming foam (AFF) agents are Known for the rapid extinguishment of Class B fires and ‘enhancement of safety by providing flashback or burnback resistance. Fist described by Francen in US. Pat. No. 3,562,156, AFFF agents by definition must have a positive ‘spreading coellcient on eyelohexane, Many US. patents describe the composition of AFFF agents which meet the positive spreading coefficient criteria, such as U.S, Pt, Nos 4,420,434; 4,472,286; 4,999,119; 5,085,786 and 5,218,021; 5616273. [0004] The prior art relating to AFFP agents has one ‘common element; the requirement of various quantities and types of fluorochemical surfactants to oblain the positive spreading coeliceat when combined with various hydro- ‘carbon surfactants. US. Pat. No. 5,616,273 describes present AFFF and aleohol resistant aqueous fil forming (AR-AFFF) agents used to generate aquoous film forming Tams having vorine contents ranging from 0.020 to 0.044 percent in premix form. The actual fori level has been ‘depeodant on the required performance specifications, with, higher Noorine content providing fester extinguishing per Jormance and greater bum back resistance. The lowest ‘Ayorine content produet (0.020% F) would contain about 1.3% by weight Muorochemieal surfactant solids in the 3% Fiquid concentrate since these products contain about 50% by weight fuorin, [0005] The criterion necessary to attain spontancous spreading of two immiscible Fiquids has been taught by Harkins et al, Journal Of American Chemistry, 4, 2668 (1922), The measure of the tendeney” for spontaneous spreading of an aqueous solution over the surface of non- polar solvents such as. hydrocarbons is defined by the spreading coefficient (SC) and can be expressed as fallow Settee whee » [0006] SC, Spreading Coelicient: [0007] yjeSurface tension of the lawer hydrocarbon phases {008} y-Suroe tension ofthe upper ago pass [0009] y.=Interfacial tension between the aqueous ‘upper phase and the lower hydrocarbon phase [0010] 1Fthe SC is postive, in theory an aqueous solution should spread and film formation on top ofthe hydrocarbon surface should occur. The more postive the SC, the greater the spreading tendoney wil be. In practice, however, it has been found that no visible film seal occurs on eyelohexane tunil the SC is greater than about +35 to about +40, ‘especially ifthe fluorochemical content is How. It is further May 4, 2006 known from the art that 7, is reduced as the temperature of the hydrocarbon is increased, a oecurs during the buraing of thse fuels. This will ower the effective SC during fre ‘extinguishing unless the fre extinguishing solution also has ‘dereasing jon increasing temperature, [0011] Fiuorochemical surfctants have recently come ‘under senutiny by the EPA and environmental groups. In fit, at least one major manufacturer recently agreed o sop the manufacture of Perfluorooctanesulfonate (PFOS) and Perfluorooctanoie acid (PFOA) based products including ‘Muorinated surfactants used in AFF and AR-AFFE agents ‘The FPA, prior to May 2000, had determined that PFOS posed a long-term threat tothe eavironmeat after PFOS was found in all animals tested and was determined to be toxie after various long-term feeding studies. The FPA has since Initiated a program requiring other perfuorochemical pro- ducers to stpply information on thelr products tothe EPA. Tis would allow the EPA to evaluate potential environmen {al problems from other fluorochemical surfactants already in the markesplace, [0012] 1 may therefore be desirable w have fire extin- ‘ishing products which do not contain fluorine-containing ‘compounds. while sill extinguishing Class B fires as ffec- tively as AFP agents [0013] The instant invention provides compositions that ‘oquire litle or no use of fuorochemical surfactants or other ‘Myorine containing compounds, yet the novel fre fighting Jiquid concentrates sill meet or exceed Fluoroprotsin (FP) ‘and Agucous Film Forming Foam agent (AFFF) perfor- ‘mance criteria on Class B, ULI62 fires If Huoeochemtcal surfactant use is severely curtailed by the EPA, these ggents could be important forthe Future of firefighting inthe United Slates, [0014] ‘The commercial APFF agent market inthe United States consists most importantly of prodoets which are UL listed such that consumers can be assured of minimum performance characteristics of AFTF agents, The UL. 162 Standard for Safety covers Foam Equipment and Liguid Concentrates. Section 3.16, UL162 (Seventh edition, 1997) defines six liquid concentrates recognized by UL. low ‘expansion liquid concentrates. Part a) defines Aqueous Fil Forming (AFEF) as “a liquid concentrate that has a fuor- nated surfactant base plus stabilizing additives.” Part b) defines Protein as “a liquid concentrate that has a hydrolyzed protein plus stabilizing additives.” Parte) defines Flor protein (FP) as “a liquid concentrate that is similar to protein, but with one or more Muorinated surfactant tives.” Part d) defines Film Forming Fluoroprotein (FFFP) as "a figuid concentrate that has both a hydrolyzed protein ‘and uorinated surfactant base plus stabilizing additives.” Pato) defines Synthetic as “a liquid concentrate that has a base other than fluorinated surfactant or hydrolyzed protein Finally Part) defines Aleohol Resistant as “a liquid eon- ccairte intended to extinguish both hydrocarbon and polar (ater miscible) fel fires. [0015] _Firewst foam application and duration to buraback fgnition is given in UI162 Table 10.1 for Class fire tess ‘These minimum performance criteria must be met fr liquid concentrates to be “UL listed” as Class B liquid concen- trates. Ofte sx liquid concentrates defined by UL. 162, only protein and synthetic donot contain fuomosurfactant and of these, cay protein has UL listed 39% products for use oaUS 2006/0091350 AI ‘Class B Figuid fires. At this time, synthetic liquid concen teates are mainly UL listed as wetting agents and defined by ULas “liquid concentrates which, when alded o plain water in proper quantities, materially reduce the surface tension of plain water and inereases ifs penetration and spreading ability Listed wetting agents solutions or foams improve the efieieney of water in extinguishing fire.” [0016] Only one synthetic, SYNDURA, commercialized by Angus Fire Armour is UL listed on Class B fires at 6% ‘chemical surfactants or fluorinated polymers, or with very Jow uotochemical surfactants or fliorinated polymer con- teat, This method provides fst extinguishment and bur back similar to that provided by FP agents, a well as, AFFF ‘agents having high fluorochemical surfactant coment. And although Class B liquid fire performanee (UL162) for such ‘agents is achieved Without requiring Muorine-contuiing ‘compounds, fiuorine-containing. compounds may’ still be used, if desired [0019] 1chas been found dat synthetic lguid concentrate ‘ean be stabilized to Class B igi fre performance (UL 162), ‘with the addition of various foam stabilizing acidic poly rie aditives in conjunction with coordinating salts. The ‘effec HIMWAP additive and th effective level necessary {or improving the synthetic quid concentrate can he readily ‘Mentified and determined through a straghtlorward fabora- May 4, 2006 tory test, Salis of interest would include those of Aluminum, Antimony. Barium, Boron, Calcium, Copper, ren, Magne ‘ium, Stontium, Thallium, Tin, Titanium, and Zine. Salts having oxidation states of #2 and 43 are most useful; and include salts of Aluminum, Boroa, Caleium, Iron, Magne- sium and Zine [0020] HMWAPs may inelude those containing multiple ‘carboxylic acid emus or other functionally acidic groups, sueh as sulfonic and phosphoric groups, Such polymers include but are not limited wo polymers or copolymers prepared by the polymerizing of monomers, which may have one or more acide functional groups thereon, and that provide hydrophobic groups, which may be inthe form of alky! branches o tails along the polymer chin of from C4 to C22 or greater. As used herein, “polymer” refers + homopolymers of copolymers, and the term “copolymer” refers to those polymers prepared from the polymerization fof vo or more dissimilar monomers. The HIMWAP may also be prepared trom linear or nonslinear polymers wherein alky! branching or als are provided afte polymerization of the main polymer chain. ‘The acidic Funetional groups may also be provided after formation of the branched polymer ‘hin, The various methods of preparation of such HMWAP. fare well known to those skilled in the ar. [0021] _Asstatod, the HMWAP have alkyl branches oF tails fof from C4 wo C22 oF greater, some or all of which may contain acidic Funetional groups. The polymers, however, ‘may contain alk] groups With ehains of C4 to C 18 length, ‘more panicularly, polymers containing multiple alkyl groups with chains of C8 to C16 length, The HIMWAP may have an averge molecular weight of from about S000 to about 2,000,000 or greater. In certsin embodiments, the HMWAP may have an average molecular of from about 20,000 or 30,000 to about 1,000,000. [0022] Effective in stabilizing the synthetic liquid eoncen- ‘rate foam bubble wo Class B liquids are HIMWAPs contain- ing hydrophobic groups, more particularly C8 to C16 alkyl substimeats including commercial peoduets, such as Chem- quand HS-100, available from Chemguird, Inc, Maasild ‘Tex. Chemguand has used HS-100 since 1999 in combina. tion with Chemguard FS-100 (Nvorinated surfactant) 10 make especially efficient AFFF agents, Chemguant HIS-100 js an HMWAP surfactant of unknown exact structure which ‘nereases foam expansion, drain time, and fhidity in the APFF formulation. In 3% AFFP agents, HS-100 is used at Jess than about 0.7% actives in all formulations to obtain ‘optimal performance and forulations typically contain only 1-2% hydrated magnesium sulfate [0023] When Chemguard HS-100 (HMWAP), which ma be asd at 249% actives, and hydrated magnesium sulfs hich may be used at approximately 530%, is used in 3% synthetic liquid concentrates, excellent Class B, UI.162 fire performance i oblained without the addition of fluoro chemical surfactants or fuorine containing compounds Unless otherise specified all percentages presented here are by weight, When HS-100 is used at the lower level, areater quantities of magnesium sulfate may be required, ‘while lower levels of magnesium sulfate are effective when higher levels of HS 100 aroused. I desired, higher levels of (Chemguard F1S-100 and magnesium sulfite may be used t0 provide even stronger performance and weaker but sll well performing products can be made wing lower quantities of these productsUS 2006/0091350 AI [0024] The composition may be wsed for providing train ing foams. An example ofa training foam product includes (09% actives Chemguard 118-100 and about 10% magne sium sulfate, which may be used as 3% taining foams. Similarly, 196 taining foams without environmental prob- Jems, except possibly for foam, ean be prepared with about 2.7% aetives Chemguard HS-100 and 30% magnesium sulfite [0025] The present invention has application wo fre extn ishing compositions useful for extinguishing ULI62 ‘Class B non-polar (Water insoluble) iquid fies by the addition of effesual HMWAP and coordinating salts 10 various synthetic liquid concentrate a elective levels. The ‘composition of IMWAP and polyvalent salts as here defined ‘could also be used in low protein content product (4 less than 10% protein by weight). [0026] The instant invention further provides a method of ‘extinguishing Clas B fies using the fie fighting composi- tions having no added Nuorochemical surfactant or ether ‘compounds containing Muorine, This method provides fat ‘extinguishment and bur back similar to that provided by FP ‘agents, a well as, APFP agents having high Muorochemical surfactant or other faorine content. The concentrates may be ‘educted at 69% oF 3% int water, citer fresh, brackish, oF se ‘water, and applied tothe fre from aspirate! or non-aspieated devices, foam chambers, or sprinkler systems. AS used herein, the term “water” may include pure, deionized or distilled Water, tap oF fresh Water, sea Water, brine, or an aqueous or waer-containing solution or mixture capable of serving as a water component forthe firefighting. compo- [0027] AFP and FP agents are known as excellent foams Jor extinguishing non-polar Class B fires; however, the presence of fuorosuefacants is seen by many asa potential ‘environmental hazard, The present invention provides a means of extinguishing these difficult fires without the we of cither uorosurfactants or other fluorine containing com= pounds and therefore does not pose an environmental az- ad, other than foam. [0028] The use of HMWAP and coordinating salts is, ‘advantageous, in part, die to the well esablished lower toxicity of polymers relative to monomeric compounds. Ia fic, it is mich easier to lst polymers (none reactive) on the TSCA inventory than low molecular weight materials due t0 this fact. Similarly in Europe, polymers are exempt from the BINICS list. It is widely understood that a6 polymers Jncrease in’ MW, their absorption rate through skin ‘dccreases. Punter, high MW polymers rapidly adsorb to solid surfaces such as dirt, rocks, ete, and are much less available for entering water ways. Therefore, they are in zeneral more environmentally benign than low MW surf fants and chemicals. [0029] The present invention is readily extended to pro= Vide fre extinguishing agents having exceptional pesfor- ‘mance ifsmall amounts of ftorosurfactants or high mole Jar weight uorinated polymers (HMWFPS), as described i US. patent application Ser- No.10/213,708 for Fire Extin- auishing or Retarding Material are included in these formu- Jations, and which is herein ineogporated by relerence. [0030] The claimed synthetic surfactant liquid compost tions may be produced at many strengths, including but not May 4, 2006 limited to 3 and 6% foam concentrates, The lowest aum- bered strengit is actully the most concentrated predic. “Therefore, three parts of 3% and 97 parts water gives 100 paris of use strength pre-min, wheres, six parts 6% and 94 parts water gives 100 parts of pre-min. [0031] |For the sake of simplicity only 3% produets willbe exemplified here, while it Js understood that many other strength produets are included, A general composition for a 3% liquid concentrate (usod at 3 parts concentrate. 97 parts Tesh or tap water) is as follows: High nolenlar weiss pobmer Bonnin t Croce Heston Sutctat EB Nonln Hyena rc areca Sica G Foams boing oleh Hiren pectin cage i Sete te, caoson ask 1 Palsene ti fone Re ie nicks [0032] ‘The above components would be reduced accord ingly relative 10 the 3% liquid concentrate to prepare 6° synthetic liquid foam concentrates {ous Most Class fam concent fi within the tion of the base surfactant defined above. ‘Therefore, fun of an elected TMIWAP ad cooing sl (a defined from the laboratory test) has application to many (Class A foam concentrates a8 well [0034] Similarly, an effectual HIMWAP and coordinating salt may also be added 1 3 or 6% liquid protein concenteate containing no oF trace flyorochemical surfactant [0035] The FIMWAP (Component A) and polyvalent coor- ‘inating salt (Component B) are chosen using the laboratory test described in the experimental section, In general these fare provuets prepared from monomers, either mono- oF polyfunctiona, polymerized with reactive polyfunetional ‘monomers, prepolymers or high MW polymers with appro- priate reactive sites, Hydrophobic and acidic sites may be ormed within the polymer hy inclasion withthe monomers or by addition to the formed polymer, such as reaction of sodium monochloroacetate with amine residues. Examples ‘of polymers for consideration using the defined performance test are described in U.S. Pat, Nos. 6,528,575 BI; 6,36],768 Bl; 6,284,855 BIL: 6,090,894: 5.039.433, 4,683,066; 4,474, 916; 4,500,684; 4,908,155; 4.317.893; 4,284,517, which are bere incorporated by reference. [0036] _A suitable commercially available HIMWAP (Com- poneat A) is Chemguard HS-100, a high MW acide polymer having multiple C12 alkyl tals and multiple eaboxsTic acid sroups. [0037] Component ft include electrolytes and eoordin ing als, add t coordinate with the above Component.US 2006/0091350 AI HMWADS to stabilize the foam bubble 10 fire and hot solvents. Typical electrolytes and salts may include those of Aluminum, Antimony, Barium, Boron, Calum, Copper, Iron, Magnesium, Stomium, Thallium, Tin, Titanium, and Zine. Salis having oxidation states of +2 and +3 are suitable. Tnchided are the alkaline earth metals, especially magne sium, calcium, strontium, and zine oF aliminu. The cations ‘of the electrolyte are not critical, except that halides may be ‘undesirable from the standpoint of metal corrosion. Sulfate, bisulfites, phosphates, nitrates and the ike are able. As used herein, the expression “coordinating salt” is runt (o inelude both salts and elecigolytes, [0038] Particularly usefin are polyvalent salts such as ‘magnesium sulfate and magnesium nitrate. [0039] The amphoteric hydrocarbon surfactants (Compo rent C) include but ate not limited to those which contain ia the same molecule, amino and carboxy, sulfonic, sulfrie fester and the like. Higher alkyl (C6-C14) betaines and sulfobetanes are included, Examples of commercially avail- able products include Chembetaine CAS and Mirstaine CS, both sulfobetaines, MacKam 2CYSP and Deriphat 160C, « C12 amino-dicarboxylate, ‘These products are excelent ‘oaming agents and help educe interfacial tension in water solution [0040] Anionic hydrocarbon surfactants (Component D) Include but are not limited to alkyl carboxylates, sulfates, sulfonates, and their ethoxylated derivatives. Alkali metal and ammonium salls may also be used. Anionic hydrocarbon ‘surfactants in the C8-C16, C8-C12, and C8-C10 range are particularly usefl [0041] The nonionic hydrocarbon surfactants (Componcat 5) help eeduce interfacial tension and solubilize other cor ponents, especially in hard water or sea water solutions. la ‘ition, they serve to control Foam desinage, foam fugit, ‘and foam expansion. Suitable noaionie surfactants include but are limited to polyoxethylene derivatives of alkylphe- ols, lincar or branched alcohols, Fatty acids, alkylamines, alkylamides, and acetylenic glycol, alkyl glyeosides and polyglycosides as described in U.S. Pat. No. 5.207.952 and ‘others, and block polymers of polyoxyethylene and polyox= ypropylene waits. [0042] Fluorochemical surfactants (Component F), whieh may be useful at fow levels, are found in the many AFFE patents including but not limited 10 those deseribed in US. Pat. Nos. $616,273, 5218021; 5,085,786; 4,999,119; 4,472,286; 4,420,434; 4,060,489, which are herein incorpo- rated by reference [0043] Small quantities of fuorochemical surfactant may be added to increase extinguishing speed and burback resistance, But in all iastanees, the total Muorochemical surfactant content is imited to less than one-half normal ‘workable levels in the absence of the inventive matter 10 provide UL 162 Class B fie performance. This means less than about 0.20% fluorine as iuorochemical surfactant in 2 3% concentrate or less than about 00696 fluorine at the ‘working strength, This compares very favorably with data of US. Pat. No, 5,207,932 leading to u commercial product ‘with low end working oorin content of 0.013% Muorine (a 535% reduction in fluorine content), [0044] Foam aids (Component G) are used to enhance oa expansion and drain properties, while providing solu- May 4, 2006 n. Usefl solvents are di at Nos. 5,616,273, 3.457.172; 322.011 ‘and 3,579,446, which are herein incorporated by relerenee. [0045] Typical foam aids are aleohols or ethers such as: ethylene glycol monoalkyl ethers, diethylene glycol ‘monoalky/ ethers, propylene glyeol monoalkyl ethers, dipro- pylene glycol monoalkyl ethers, ethylene glycol ponoalky] eters, I-butoxyethoxy-2-propanol, glyeerine, ‘and hexylene glyco. [0046] The treeze protection package (Component F) may fnclude glycerine, ehylene glycol, diethylene glycol, and propylene glycol. Also included are salts and other solids ‘which reduce freeze point sch as calcium, potassium, sodium and a [0047] Component 1, the sequestering, buller, and corro- sion package, ae sequestering and chelating agents exem- plified by polyaminopolyearboxylic acids, ethylenediamine fetraacetic acid, citric acid, tartaric acd, nitilotracetic acid, dbydroxyethylethylenediaminetriacetic aid and salts thereot. [0048] | Butlers are exemplified by Sonensen’s phosphate ‘or Mellvaine’s citrate bullers, Corrosion inkibitors are only limited by compatibility with other formula. components ‘There may be exemplified by ortho-phenylphenol, toluyl triazle, and many phosphate ester acids, [0049] Components J is @ water soluble polymeric film ormer ane! may be used forthe formulation of AR (aleohol resistant) agents which are usod to fight both polar (water soluble) and non-polar solvent and fuel fires. These poly- eric film formers, dissolved in AR agents, precipitate from solution when the bubbles contact polar solvents and fuel, and form a vapor eepelling polymer film a the solvent! foam interlace, preventing further foam collapse. Examples of stituble compounds include thixotropie polysoecharide saums as described in US. Pat, Nos, 3.957,657; 4,060,132; 4,060,489; 4,306,979; 4.387.032; 442034: 4,424,133; 4464267, 5,218,021, and. 5,750,043, which are herein ‘incorporated by reference, Suitable commercially available compounds are marketed as Rhodopol, Kelco, Keltol, Actigum, Cecal-gum, Calaxy, and Kalzan. [0080] Gums and resins useful as Component J include acidic gums such as xanthan gum, pectic acid, alginic acid, ‘gar, carrageenan gum, shamsam gum, welan gum, mannan Zum, locust bean gm, galactomannan som, pectin, starch, bacterial alginic acid, succinoglucan, gum arabic, car boxymethyleelulose, heparin, phosphoric acid polysscch- ride gums, dextran sulfate, dermantan sulfate, focan sulfate, ‘gum karaya, gum trgacanth and sulfate locust bean gum [0081] Neutral polysaccharides wsefil as Components J include: cellulose, hydroxyethyl cellulose, dextran and ‘mosified dextrans, neutral glucans, hydroxypropyl cell lose, as well, as other cellulose ethers and esters, Modified starches include starch esters, ethers, oxidized starches, and enzymatically digested starches. [0082] Components K, antimicrobials and preservatives, ray be used to prevent biological decomposition of natal product based polymers incorporated as Components J Inchided are Kathon CG/ICP and Givgard G-4-40 manufac tured by Rohm & Haas Company’ and Givaudan, Ine respectively, as disclosed in U.S. Pat. No. 5.207.932. Addi- ‘ional preservatives are disclosed in the above polar ageUS 2006/0091350 AI patents—US. Pat Nos. 3,957,657: 4,060,132; 4,060,489; 4306,979; 4,387,032; 4420434, 424,138; 4.464.267. 5.218021, and 5,750,043, which are herein incorporated by reference, [0083] Components L are polymeric foam stabilizers and thickeners which ean be optionally incorporated into AFFE ‘and AR-AFFF agents to enhance the foam stability and foam ‘drainage properties. Examples of polymeric stabilizers and thickeners are partially hydrolyzed protein, starches, poly- vinyl resins such as polyvinyl alcohol, polyacrylamides, cearboxyviny! polymers, polypyzotidine, and polyoxyeth- lene) glycol [0084] Many commercial synthetic surfactant concen- trates are marketed worldwide by Chemguard, Kidde, and ‘Tyco. The addition ofan effectual high MW acidic polymer and coordinating salt to these liquid concentrates at an ‘ellective concentration may be encompassed by the resent ‘invention. These products include: Class A foams (CLASS A PLUS and SILVEX), excellent for extinguishing forest fires, structural fires, and tte fies; High expansion foams Sold’ under the names HI-EX, EXTRA, C2, and VEE- FOAM: Vapor suppressant foam sold by Chemguand as ‘VRC feam: Bomb foam, a 6% product sold by Chemguard ss APC-380, [0085] Synthetic surfactant concentrates listed as “wetting ayents” by Underwriters Laboratory are aso included as base surfactant mixtures for use inthis invention, Products listed by UL as “weting agents” include the following: Fire Surke by Biocenter Inc. Bio-Fire by Envirorenu Technolo- ies LLC; Enviro-Skin 1% by Environmental Products Ine .500 by Hazard Contr Technologies Inc; Knockdown by National Foam Ine; Phos-Chek WD8SI_ by Sol Flameout by. Summit Blazeout by Verde Environmental Ine; Bio-solve by West- Jord Chemical Comp. EXAMPLES [0056] In the examples below, references are made to specifications used by the industry to evaluate the eliiency ‘of synthetic surfactant concentrates. More specifically. the ‘examples refer to the following specifications and laboratory test methods! [0087] Surface Tension and Interfacial Tension: According fo ASTM D-1331-56, Based on laboratory tests, the surface tension of eyelohexane used for calculating the SC was 24.7 dynesiem, [0088] ‘The UL 162 Type IIL, Class B, topside ie test for AFFF agents was used 10 test the 3%6 synthetic liquid ‘concentrates as premixes in tap water and synthetic sea water. For each fre test, 5S gallons of heptane was charged to a 50 A heavy stesl UL pan with enough water in the bottom t give at least eight inches of sideboard. A US nilitary type aspirating nozzle adjusted to give a 2.0 gallon per minute flow rate was placed on a stand. The fire is lit, allowed 10 burn for 60 seconds, and then foam is directed ‘onto the surface of the fuel until the fie is about 75% ‘extinguished, Then a firefighter picks up the nozzle and ‘moves the Foam stream back anl forth until 90% extinguish- ‘ment (contol time) is obtained, at which time the firefighter js allowed to fight the fire from two sides ofthe pan. Times fare recorded at 9% contol and at extinguishment. Foam application is continued fora total of 3 minutes. May 4, 2006 [0089] At about 8 mis es, 4 L.0 square foot steel stove- Pipe is placed 1.0 {t from each side of the comer last ‘extinguished and all foam iaside the pipe is removed. After ‘waiting 9 minutes from foam shut-of, the fuel inside the pipe is it and allowed burn for I minute. The pipe i thea ‘removed und liming ofthe buraback is started. When the fre increases t0 20% of the pan area, the bumbock: time is recorded, [0060] Foam quality is measured by taking the expansion ratio and drain time from the nozzle after naing the fire [0061] An AFFF product passes this fire test by extine ‘ishing before 3 minutes and having a bumback equal t oF rcatr than 5 minutes. Stronger pracucs give shorter extin- fishing and longer buraback tints, [0062] The UL 162 Type II, Cass B, topside, fre test for Fluoroprotein (FP) agents wat used to test the 3% synthet Iiquid concentrates as premixes in tap water and synthetic sea water For cach fie test, 55 gallons of heptane was charged to a 50 f¥ heavy steel UL pan with enough water in the botlom to give at last cight inches of sideboard. A US nilitary type aspirating nozzle adjusted to give a 3.0 gallon pet minute flow rate was placed on a stand, The fire is lit Allowed to bum for 60 seconds, and then foam is directed ‘onto the surface of the fel until the fire is about 75% inguished. Then a freighter picks up the nozzle and noves the Toa stream back and eel Until 90M extinguish ‘meat (contol time) is obtained, at which time the firefighter js allowed to fight the fire fom two sides ofthe pan, Times are recorded at 902% control and at extinguishment. Foam application is continued for a total of 5.0 minutes [0063] At about 14 minutes,» 1.0 square foot steel stove- pipe is placed 1.0 1 from each side of the comer last ‘extinguished and all foam inside the pipe is removed. After waiting 15 minutes from foam shut-ol, the fuel inside the pipe is lit and allowed to burn for I minute. The pipe i thea ‘removed and timing ofthe Burnback is started. When the fre increases 10 20% of the pan area, the burnbock time is recorded [0064] Foam quality is measured by taking the expansion ratio and drain time from the nozzle after nning the fire test, [0065] _A FP product passes this fre test by extinguishing before 5.0 minites and having a bumback equal to or greater ‘han 5 minutes. Stronger products give shorter extinguishing ‘ad longer Bumaback ines, It should he noted that FPs whea ‘compared with AFFE agents are applied ata rate of 06 vs (0.04 galt and for two minutes longer than AFF agents: 9 Jonger bumbsck of 21 minutes minimum i roquted for FPs versus 1S minutes for AFFF agents [0066] Simple 39% synthetic suefactam concentrates were formated to demonstrate the invention; Examples A-H are given below in Table I to show performance enhancement ‘dae to HIS-100/Magnesini sulfate interactions [0067] ‘The Chemguard H1S-100 used as the anionic hydro- ‘arbon sueTactant is that manufactured by Chemguard Inet 445% solids in water. Chombetaine CAS is used at a 50% solids cocoamidopropyl hydroxypropyl sulfobetane, and is ‘available from Chemin, Mackam 2CYSP is 50% solids ‘ety! dipropionate from Melntyre while Deriphat D-160C isUS 2006/0091350 AI 30% solids lauryl dipropionate from Henkel. Sulfoehem NADS is 30% solids sodium decyl sulfite in water from ‘Chemroa, Sulfochem NOS is 40% solids sodium octyl sulfate in water from Chemmon, Witeolate 7103 is 60% solids ammonium lauryl ether sulfite from Witeo. Magne- sium sulfite is charged as the heptahydrate. TABLE la. tame as 18 27 38 26 38 36 Chentenine 0S aS OS OS OS OS OS OS Silfetem 60406 6D. «6-46 ADs scot ae os Mipesiam 90-200 140 9 490 200 100 50 ‘wer As Ms $97 Ss 99 #9 TD wD er Succ ns ma ud m9 mo 27 Te 0 “ee Smaing! 7 19 20-15-19 as a7 a3 “ie dyn i imei enson at eobaane [0068] TABLE 1b Sumas Hew as 0 ae as as wT feNteAP) NiStsion san mo 309 m9 300 wo 90 mo May 4, 2006 {0069} TAMLE te coe ost eerie ligwwacisie Ga ta 0a ala Craewae seo Nest 3018" tty ua ts as woes 73 rn rar {o07} TABLE 2 {O12 Type Cae By Hee Fi Te Uap Sous a0 gl Megseium 300300 340 3h 300. 200 100 30 Sie b9) Hegane. "F867 an so Coot) Time? None 18 1.8 1 10 10 18. Bumps 9% 36M 2 a ea “S Frum boos 27 as An Se Ss Be [oo71) TABLE 2b ‘OL 162 Type Cae Bap i Tn, Than Sun adel Asa fee oe ek «a aUS 2006/0091350 AI [0072] TABLE 2e ‘UL 162 Type MCs Bape Fe i Dd Ot ears re vv Hepa, °F 2 3p as [0073] Fxamples A through F (Tables 1a and 2a) demon- mt a definitive improvement in ULI62 type performance When the FIS-100 content is increased from 0 10 3.6% while holding the magnesium sulfate content constant at 30% all ‘ther formula components are held constant. In feet, Example A without HS-100 did aot control the fie (0% ‘extinguishment at 5.0 minutes) while Example E extn: ‘auished at a rapid 1.9 minutes, had 100% foam cover at burback time, and had 4.1. minutes buenback; vast ‘improvement on ineeasing H1S-100 concentration. Cleary, the performance improved with each inerease in the HS-100 ‘content going from Example A through E-whea the magne= sium sulfate content was held at 30%. Since all other ‘components were held constant, tbe UL 162 type perfor- ‘mance improvement must be due to the HS-100; high ‘molecular Weight anionic polymer. [0074] Prom Examples A-F itean be seen that there is no ‘correlation between the spreading coefficient (SC) and the fire performance of the formulations, Example A with the Jeast-negative SC had the poorest performance, while Example E had a negative 1.9 SC and performs bes in the series It can be reasoned that the fire performance is independent of the SC. Therefore, the interaction between the HMWAP and potyvalent salt rmust stabilize the foam bubble to the flame andl hot fuel rather than enhance the surface ative properties. Examples E-ll and 1, 3 [0075] Examples & through #1 (Tables 1a and 25) show 3 “dramatic redction i performance asthe magnesium sulfate ‘content was reduced from 30% to 59% in inerements while holding the HS-100 content at 3.69%, In fact, Example H ‘with only 5% magnesium sulfate and 3.69% HS-100 (a high Jevel) would extinguish the fre, but at burmback time only 29% ofthe pan was covered with foam, Therefore a bumback ‘could not be run. Certainly, UL 162 fire performance decreased with each reduction in the magnesium sulfite ‘content May 4, 2006 [0076] The SCs of Examples F-tl, as above, did not correlate with the fire performance ofthe formations. It ‘mus agi be concluded thatthe surface active properties do ‘ot contol the fie performance characteristic ofthe Wor ing invention, [0077] Pxamples | and J illustrate two formas wsilizing Mackim 2CYSP instead of Chembetsine CAS, where Example I contains 3.6% H1S-100/30% magnesium sulfete and J has 0% HS-10030% magnesium sulfite. As in the ‘examples above (F8:.A), even with a high magnesium sulfate content Example J without HS-100 would not even extin- auish the fire while Example | performed well. Clearly. strong ULIG2 fire performance requires that both HS-100 ‘and magnesium sulfate be at effective levels [0078] However, various combinations of HS-100 and ‘magnesium sulfate were soon to provide enhanced fire performance. Example G with 3.6% 11S-100/10%% msagne- sium sulfate demonstrated approximately equivalent pero ‘mance 10 previously presented Example D with 2.7% HS-100/30% magnesium sulfate. Therciore, excellent per- Tormance is obtained from lower HS-100 content forme sions if higher quantities of magnesium sulfate are used, [0079] It should be noted that even at 3.6% FIS-10005% ‘magnesium sulfate and 0.9% FS-100/30% magnesium sul- fine, the fires were extinguished at 3.0 and 3.6 minutes: demonstrating the effectiveness of larger quantities of TS-100 in the presence of low levels of magnesium sullate or visa verse. Higher quantities of either HS-100 or mag- esium sulfite are required for obtaining acceptable burn- back performance, Examples K-M (Tables Ib and 26) [0080] Example K is varied from Example E by only replacing Chembetaine CAS with Mackam 2CYSP at a higher actives level. It can be seen that Mackam 2CYSE works well as a replacement for Chembetaine CAS since both formulations had excellent extinguishment and burn- bck performance. Examples K-M demonstrate the effect of turther increasing levels of amphoteric hydrocarbon surfae- ‘tant on UL 162 fire performance. Examples K-M represent a series with increasing levels of Mackam 2CYSF ampho- terie surfactant, The best performance overall was obtained by Example L with 2.89% Mackam 2CYSF. It should be noted that Fxample [passed all specifications for the UL 162 fre test including the burnback which requires a mini- sum of S minutes forthe bumback. Examples N-P (Tables tb and 2b) [0081] | Fxamples N and O compare formas having dif ferent anionic hydrocarbon surfactants atthe same actives ‘content, I can be soon that 7.5% aetives Silfochem NADS (Godiuma decyl sulfate, Example N) and Witeolate 7103 ammonium dodeeyl or lauryl ether sulfite, Example O) provide equivalent fire perlommance. Therefore, sodium ‘decyl sulfate and ammonium dodecyl ether sulfate work 10 provide similar performance in these fommulations. [0082] _Fxample P exemplifies a very diferent hydrocar bon surfactant mixture with 4.8% actives Deriphat 1600, @ sodium lauryl sulfate amphoteric, and 2.0% actives Sulla- cheat NOS, sodium octyl sulfite. Although extinguishment was somewbat slower and bumback was shorter than forUS 2006/0091350 AI Examples N&O, good performance was stil obtained for such a large change in the base formula when the HS-100 ‘and magnesium sullate contents were 3.6% and 30%, respectively, Examples Q-S(Tables 1 and 26) [0083] Fxamples A-P refer to UL fre tests based on the Eluoroprotein (FP) fire tet procedure with foam applied at 3 gpm (0.06 gal?) for $ minutes. Examples Q-U were tested using the AFFF test regime of 2 epm (0.04 gal) for 3 minutes; a tougher test procedure since only 6 gallons of premix is used versus 15 gallons forthe FP test. Pxamples ‘QS exemplify the importance of HS-100 and magnesium sulfate for obtaining AFFP type UL. 162 fire performance. As S100 is reduced from 2.3% (Fx. Q) 1 14% (Fx. R) and finally 0% TIS-100 (Fx. 8), the performance went from ‘excelent, fo moderate, 10 poor. Example Q, bowever, was a Strong product meeting all UL 162 fre perlomnance resire= ments Even at 39% less HS-100 content, Example R ‘extinguished the fire st 2.5 minutes and gave 1.9 mites of bumback time, Only ai 0% HS-100 did fire performance properties diseppecr. [0084] It should be further noted that for Examples Q-S, fo solvent was included in the formulation to enhance of Sabilze foam, yet excellet foam quality was produced. Therefore, itis clear tht these formulations do not require the addition of solvent foun boosters Examples T-V (Tables Le and 2e) [0085] Examples TSU are similae wo Example Q, but have the addition of a solvent foam stabilizer, hexylene glyecl ‘and have varied levels of Mackam 2CYSF and Sulfochem NADS, Examples TSU ean be saen in Table 2e to provide ‘exceptional extinguishment at only 1.8 minutes and burn= back times greater than 80 minutes with tap water Example U when tested with sea water gave an extinguishment of 2.3 mines and 6.8 minutes for burmback; still excellent per formance. [0086] Example V demonstrates excellent performance in fea water without the use of a foam stabilizer and with only 15% magnesium sulfate. Extinguishment was fess than 2 rmiinutes and burmback time was grater than 8.0 minutes, [0087] These examples demonstrate that the combination ‘ofa HMWAP and a polyvalent salt provides UL. 162 Class B fire performance using either the AFFF or FP standard ‘conditions, [0088] The UL162 Type IIL, Class B fire test recognizes 2 difference between AFTF and FP type fire extinguishing ‘agents. AFFF agents must extinguish in 3.0 minutes or ess an application density of only 0.04 gal? while FPagents only need to extinguish in 5.0 minutes at an application density of 06 gal, This means 6.0 gallons of premix are used for AFEF while 15.0 gallons of premix are applied for EP agents. As noted above, however, the burabaek requine- ments for FP agents aee more severe thaa for AFFE agents FP agents must have a minimum of 21 minutes buraback {rom time of foam shutoff compared to 1S minutes minimum bumback for ATP agents, [0089] The firefighting compositions as described herein, ‘ay be applied to non-polar liquid hydamcarbons to extin~ uish or retard fires from sueh liquids during burning. The May 4, 2006 composition may be applied both to the surfice of sueh liquids or may be introduced below the surface, sucl as through injetion. The composition may be applied in com- bination with other fire fighting agents, sf necessary, such as the dual-ogent application of both foam and a dry chemical or powder fire fighting agents. An example of such a dry chemical or powder agent is that available commercially as Purple K. In such dual application, the fire ighting agents ‘may be applied through the use of adjacent of as generally concentric nozzles, In some instances, the dry or powder ‘agent may be applied alone to initially extinguish any Name, ‘with dhe foam bei applied to prevent reigniting ofthe fue. [0090] While the invention has boen shown in only some ‘ofits forms, it should be apparent to those skilled inthe at tat it isnot so Timited, but is susceptible to various changes and modifications without departing from the scape of the invention. Accontingly, itis appropriate that the appended claims be construed broadly and ina manner consistent with the scope of the invention. 1 claims 1A method of extinguishing or retarding a fire compeis- ing: providing a fie fighting composition comprising water, 3 high molecular weight acidic polymer (HMWAP), a hydrocarbon surfactant and a coordinating sa, the fire ighting composition mesting UL 162, Class B perfor mance ertera for at least one of AFFF agents and fMuoroprotein (FP) agents. without requiring organic ‘wore aad tha does not form a stable seal on eyelo- hexane; and applying the composition to an area where extinguish ‘meat oF retardation of the fire is desired 2. The method of claim 1, further comprising: applying the composition to the area in combination with 's dey firefighting agent 3. The method of claim 1, wherein: the HMWAP fas an average molecular weight of atleast 5000 g/mol 4. The method of claim 1, wherein: the fire Aighting composition moots UL. 162, Class B. performance criteria for both AFFP agents and Muoro- protein (FP) agents without requiring organic fluorine 8. The method of claim 1, wherein: the fre fighting composition has from about 0.01 to abot (03% IIMWAP by weight of the fire fighting compo- 6. The method of claim 1, wherein the fire fing composition has from about 0.1 f© about 1.5% of the coordinating salt by weight of the fire Fighting composition 7. The method of elaim 1, wherein the fire fighting composition contains a fuorochemical surfctant that provides less than about 0.006% fluorine by weight of the firefighting composition 8. The method of claim 1, wherein the fire fighting composition has a spreading coefficient ‘against cyclohexane of 2210 oF lessUS 2006/0091350 AI 9. The method of claim 1, wherein: the fire fighting composition has from about 0.01 to about (0.3% HIMWAP by Weight of the fie fighting compo sition, and whorwin the fie fighting composition has from about 0.10 to about 1.5% ofthe eoondinating salt by weight of the ire fighting composition, 10, The micthod of claim 1, wherein: the coordinating salt includes those selected from sats and clectolytes of aluminum, antimony, barium, ‘boron, calcium, copper, iron, magnesium, calcium, siroatium aad zine 11. The method of claim 1, wherein the HMWAP inchides those polymers having C4 to C22 alkyl branching, 12. The method of claim 1, wherein: the fire fighting composition includes at leat one of a Nluorochemical surlactant, an amphoteric hydrocarbon srfacta, an anionie surfactant, « nonionic surfactant, 4 foaming aid, freeze protection agent, a sequestering ‘agen, a bullering agent, « corrosion inhibitor, a poly- meric film former, an antimicrobial agent, a preserva tive, a polymeric fos stbilizer and a polymeric foam thickener 13. The method of claim 1, wher the coordinating salt is a polyvalent sat 14, A method of extinguishing or retarding @ fe com- prising: providing a foam concentrate comprising water, high ‘molecular weight acdie polymer (HMWAP), a hydro- carbon surfactant and a coordinating salt ixing the Foam concentrate with water to form a fire Fighting composition meeting UL. 162, Class B perfor mance erteria for at least one of AFFF ageats and Auotoprovein (FP) agents without requiring organic ‘uorine and that does not form a stable seul on eyelo- hexane: and applying the composition to an area where extingwish- ‘mentor retardation of the fie is deste 15. The method of claim 14, wherein: the foun concentrate has a HMWAP content tha provides ‘te fire fighting composition with from about 0.01 t0 about 0.3% HMWAP by weight of the fire fighting ‘composition. 16. The method of claim 14, wherein: the foam concentrate has @ coordinating slt content that ‘provides the firefighting composition with from about (0.1 to about 1.5% of the coordinating salt by weight of the fire fighting composition, 17. The method of elaim 14, wherein: the foum concentrate includes « Aorockemical surfc- ‘tant, and wherein the foam concenteate has @ fluorine Ccantent provided from the uorachemical that provides the fire fighting composition with less than about 0.006% fluorine by weight of the firefighting compo- May 4, 2006 18, The ‘the foam concentrate is used in an amount of from aboot 1 to about 10 parts concentrate to about 90 to about 99 pars water to form the firefighting composition, 19, The method of claim 14, wherein: wtbod of claim 14, wherein: the HMWAP tas an average molecular weight of atleast 5000 g/mol 20, The method of claim 14, wherein 12 amphoteric hydrocarbon sur- ionic surfactant, noaionie surfactant, 2 foaming sid, a freeze protection agent, a sequestering ‘agent, a bullering agent, a corrosion inhibitor, a poly meric film former, an antimicrobial agent, a preserva tive, a polymeric foam stabilizer anda polymeric foam thickener. 21. The method of claim 14, wherein: factant, the fire fighting composition moots UL. 162, Class B. ‘performance criteria for both AFFP agents and foro protein (FP) agents without requiring organi fluorine 22, The method of claim 14, wherein: the firefighting composition has a spreading coellicient, ‘against eyelohexame of zero oF Iss 23. The method of claim 14, wherein: the fire fighting composition has from about 0.01 to about (03% HIMWAP by weiaht of the fie fighting compo- sition, and wherein the fre fighting composition has from about 0.10 to about 1.5% ofthe coordinating salt by weight of the firefighting composition, 24. The method of claim 14, wherein: the coordinating salt includes those selected from salts ‘and electrolytes of aluminum, antimony, barium, horon, calcium, copper, iron, magnesium, calcium, strontium and zine 2S. The method of claim 14, wherein: the HMWAP inchides those polymers having C4 to C22, alkyl branching 26, The method of cli the coordinating salt isa polyvalent sat 27, A method of extinguishing or retarding a fire com- prising: providing a firefighting composition comprising water a high molecular weight acidic polymer (HMWAD) hav ing an average molecular weight of atleast $000 g/mel, ‘a hydrocarbon surfactant anda polyvalent coordinating salt, the fie fighting composition meeting UL 162, Class B performance criteria for at least one of AFF ‘agents and fluoraprotein (FP) agents without requiring ‘rganie flaorine and that does not form stable seal on cyelohexane, and 14, wherein applying the composition to an area where extinguish: ‘ment or retardation of the fre is desired.