US 20050001 197A 1 c2) Patent Application Publication co Pub. No.: US 2005/0001197 AL «i» United States Clark (54) FLUORINE-FREE FIRE FIGHTING AGENTS. AND METHOD (79) Inventor: Kirtland P. Clark, Mansfild, TX (US) Correspondence Address: GRADY K. BERGEN 2626 COLE AVENUE SUITE 400 DALLAS, TX 75204 (US) (21) Appl. Nos 10/600,810 (22) Filed Jun, 20, 2003 (43) Pub. Date: Jan. 6, 2005 Publication Classification (1) Incl? A@2D 10 @) US.CL 2823 on ABSTRACT ‘A foum concentrate provides a fire-fighting composition ‘when mixed with water so that the fie-ightng composition does not form a stable seal on eyelohexane and moets UL 162, Class B performance eviteria for at least one of AFF agents and fluoroprotein (FP) agents without requiring ‘rganie fluorine. The concentrate is Formed from water and {high molecular weight acidic polymer (HMWAP) and & ‘oondiaating saltUS 2005/0001197 Al FLUORINE-FREE FIRE FIGHTING AGENTS AND METHODS, ‘TECHNICAL FIELD [0001] The invention relaws generally to fire-fighting agents BACKGROUND {0002} Aqueous film forming foam (AFFF) agents are known for the rapid extinguishment of Clase Bt fires and ‘enhancement of safety by providing flashback or buraback, fesistance. First described by Francen in US. Pat. No. 3,562,156, AFTF agents by definition must have a positive ‘spreading’ coclicient on cyclohexane. Many US patents describe the composition of AFFF ageats which meet the positive spreading coefficient criteria, suchas U.S, Pt, Nos $420,434; 4,472,286; 4,999,119; 5,085,786 and 5,218,021; 5,616,273. [0003] The prior art lating to AFFE agents has one ‘common element; the requirement of various quantities and types of Huorochemical surfactants to oblain the positive spreading coefficient when combined with various hydo= cearbon surfactants. US. Pat. No. 5,616,273 describes present AFFF and aleohol resistant aqueous film forming (ARAFFF) agents used 10 generate aqueous film forming foams having fluorine contents ranging from 0.020 to 0.044 perevot in premix form, The actual fluorine level has bee ‘dependant on the required performance specifications wil higher Muorine content peoviding Taster extinguishing per formance and greater buen back resistance. ‘The lowest fluorine content product (0.020% F) woul contain about 1.3% by weight Nuorochemieal surfactant soli in the 39% Tiguid concentrate since these products contain about 50% by weight uorine [0004] The criterion necessiey to attain spontaneous, Spreading of two immiscible liquids has been taught by Harkins et al, Journal Of Americun Chemistry, 4, 2665 (1922). ‘The measure of the tendeney for spontaneous, Spreading of an aqueous solution over the surfice of pon- Polar solvents such as. hydrocarhons is defined by the ‘spreading coelicient (SC) and can be expressed a follows: SCamtotite mice » [0005] SC, »Spreading Coclciens [0006] y,-Sueface tension of the lower hydrocarbon phase; [0007] y,=Surface tension of the upper aqueous ‘hase; and [0008] Interfacial tension between the aqueous ‘upper phase and the lower hydrocarbon phase [0009] If he SC is positive, in theory an aqueous solution ‘should spread aed film formation on top of the bydrocacbo surface should occur. The more positive the SC, the greater the spreading tendeney wil be. In practice, however, it has heen found that no visible film seal occurs on eyelohexane until the SC is greater than about +3.5 10 about 4.0, espe- cially if the fluorochemical content is low. Tt is further Known from the at that y i reduoed as the temperature of| the hydrocarbon is increased, as occurs during the burning ‘of these fuels. This will lower the elfective SC during fice Jan. 6, 2005 [0010] Fluorochemical surfactants have recently come tinder scrutiny by the EPA and environmental groups. In Tact, at least one major manvfacturee recently agreed 0 slop the manufacture of Perfiuorooctanesulfonste (PFOS) and Perfluorooctanoie acid (PFOA) based products including ‘vorinated surfactants used in AFFP and AR-AFFF agents, The EPA, prior to May 2000, had determined that PFOS posed a long-term threat tothe environment after PEOS was ound ia all animals tested and was determined 10 be toxie fier various long-term feeding studies. The EPA has since initiated a program requiring other pertuorochemical pro- ducers to supply information on their precicts tothe EPA. ‘This would allow the EPA to evahuate potential enviconmen- {al problems from other uorochemical surfactants already in the marketplace. [0011] It may therefore be desirable 10 have fire extin- {uishing praduets whiel do not contain fuorine-containing ‘compouas, while still extinguishing Class B fires as effec tively as AFFF agents [0012] |The instant invention provides compositions that ‘equi lttle or no use of uorochemical surfactants or other ‘fuorine coatsining compounds, yet the novel fre fighting liquid concentrates sill meet or exceed Fluoroprotein (FP) and Aqueous Film Forming Foam agent (AFF) perfor- ‘mance criteria on Class B, UL162 fies. If uorochemieal surfactant use is severely curtailed by the EPA, these agents couldbe important ore favoring he Unied States, [0013] ‘The commercial APFF agent market inthe United States consists most importantly of products which are UL. listed such that consumers can be assured of minimum performance characteristics of AFEF agents, The UL. 162 Standatd for Safety covers Foam Equipmeat and Liquid Concentrates. Section 3.16, UL162 (Seventh edition, 1997) Sefines six Tiguid concentrates ecognized by UL. as low ‘expansion liquid concentrates. Part a) defines Aqueous Film Forming (AFFF) as a liguid conevoteate that has 2 fluor rated sucfaclant base plus stabilizing additives.” Part b) efines Protein as“ liquid concentrate that basa hydrolyzed protein plus stabilizing additives.” Part c) defines Fluoro- protein (FP) as “a liquid concentrate that is similar to protein, but with one or more forinated surfactant add tives.” Part) defines Film Forming Fluoroprotein (FFFP) as "a liquid concentrate that has both a hydrolyzed protein land fluorinated surfactant base plus stabilizing additives” Parte) defines Synthetic as “a liquid concentrate that has 2 base other than fluorinated surfactant or hydrolyzed protein Finally Part 1) defines Aleobol Resistant as “a liguid eon- centrate intended to extinguish both hydrocarbon and polar (Gvater miscible) fuel fires.” [0014] Fire test foam application and duration to buraback Jgnition is given in UL 162 Table 10.1 for Clas B fire tests Tse minimum performance eriteria must be met for liquid concenteates to be “UL listed” as Class B liquid concen- trates, Of the six liquid concentrates defined by UL. 162, only protein and synthetic do not contain luorosurfactant and af these, only protein has UL listed 3% products for use’on (Class B liquid fires. At this time, synthetic liquid concen- trates are mainly UL listed as wetting agents and defined by ULas liquid concentrates which, when added to plain WaterUS 2005/0001197 Al in proper quantities, materially educe the surface tension of| plain waler and increases iis penetration and spreading ability. Listed wetting agents solutions or foams improve the ellciency of water in extinguishing fires.” [0015] Only one synthetic, SYNDURA, commercialized by Angus Fite Armour is UL listed on Class B tires at 6% dilution rate and at the Guoroprotein application rate. Syn- ‘dura utilizes a polysaccharide stabilizing agent, and although marketed as “operationally Quorine-fee,” it des ‘contain a Teast some Auorine DETAILED DESCRIPTION [0016] The present invention provides fire fighting com ‘centrates of the synthetic type which meet and exceed UL listing requicemenis for use on Class B fies as listed ia UL162 that may have “zero” fluorine content. Further, these products may be used at 3% concentrate level, No fuoro- ‘Surfactants or tluorinated polymers are required to meet the UL162 standard but may be used to improve extinguishing ‘peed and burnback times, if desired. The compositions for Use as fre extinguishing concentrates can meet or exceed luoroprotein (FP) and! ARFF performance exiteris on Class B, ULL62 non-polar (water insoluble) liquid fres, but with- ‘out the need of fluorachemical surfactants or polymers, a5 tequired in the prior art. These compositions include sya- thetic liquid concentrates stabilized with high molecu ‘weight acidic polymers (HMWAP) and coordinating sal(s), ‘which extinguish non-polar Class B fires. No fluoresurlac™ {ants or fuorinated polymers are required to meet the UL, 162 standard, but may be used to improve extinguishment speed and burnback times, I desired. Thus, as used herein, the expression “without requiring fluorine” or “without requiring organic fhorine” is meant to cover those situations ‘wlirein the composition provides the stated performance absent such fluorine or ofganie fluorine components that ‘ight otherwise he included, with all ether components and felative quantities of such eomponents (other than the speci fied Buorine) remaining the same, and does not preclude that fluorine or organic fuorine may'be ineluded in such com- positions [0017] The invention futher provides 4 method of extin- ‘uishing Class B noa-polar liquid tres using the fire fighting ‘compositions without requiring or having no add luoro- ‘chemical surfactants or luocinated polymers, or with very low uorochemical surfactants or IMorinated polymer con- teat, This method provides fast extinguishment and burn- back similar to that provided by FP agents a well as, AFFE agents having high fluorochemical surfactant content. And although Class 1 liquid fire performance (UL162) for such agents is achieved without requiring luorine-containing ‘compounds, luorine-coutaining compounds may sill be used, if desired [0018] 11 has been found that synthetic liquid concentrate ‘can be stabilized to Cass B liquid fre performance (UL 162) with the addition of various foam stabilizing acidie poly- ‘meric alives in coajunction with coordinating salls. The ‘Ase Hydocbo Surat Zp e NonieHyrocuton sun a F Forecast! Suicer, boa in Fees proton pctase bas t ‘Seneca, but consin pecags OS 1 Palms i forme ba t Paty ously an thikenen Oo10 [0031] The above components would be reduced accord ingly relative to the 3% liquid concentrate to prepare 6% synthetic liquid foam concentrates [0032] Most Class A foam concentrates fit within the ‘efiition of the base surfactant defined above. Therefore, tition ofan effectual HMWAP and coordinating sult (1s efined from the laboratory test) has application to many (Class A foam concentrates as wel [0033]. Simitacy, an effectual HMWAP and coordinating salt may also be added to 3 or 6% liquid protein concentrate onining no oF trace fuorochemical surfactant [0034] |The HMWAP (Component A) and polyvalent coor- ‘inating salt (Componcat B) are chosen sing the laboratory test described in the experimental seeton, In general these are prosluets prepared from monomers, either mono~ or polyfunctonal, polymerized with reactive polyfunetional ‘monomers, prepolymers or high MW polymers with appro- priate reactive sites. Hydropbobie and acidic sites may be ormed within the polymer y inclusion withthe monomers ‘or by adultion to the formed polymer, sich as reaction of sodium monochloroacctate with amine residues. Examples of polymers for consideration using the defined performance test are described in US, Pat, Nos. 6,528,575 BI; 6.361,768 Bi; 6,284,855 BL; 6,090,804; 5,039,433, 4,683,066; 4.174, 916; 4,500,684; 4,908,155; 4.317.803; 4,384,517, which are bere incorporated by reference [0035] _A suitable commercially available HMWAP (Com- ponent A) is Chemguard HS-100, a high MW acide polymer bbaving multiple C12 alkyl als and motile caboxdlie acid groups. [0036] Component B include electrolytes and coordinat- ing salts, added to coordinate with the above Component A. HIMWAPs to stabilize the foam bubble to fire and hot solvents. Typical electrolytes and salts may include those of| Aluminum, Antimony, Barium, Boron, Calcium, Copper,US 2005/0001197 Al Iron, Magnesium, Strontiu Zinc. Salis having oxidation Tnchided ace the alkaline earth metals, especially magne- ‘sium, calcium, strontium, and zine or aluminum. The cations ‘ofthe electrolyte are not eitical, except that halides may be undesirable Irom the standpoint of metal corrosion, Sulfates, bisulfates, phosphates, nitrates and the like are also accept> able. As used herein, the expression “coordinating silt” is ‘meant inelude both salts and electolytes [0037] Particularly useful are polyvalent sas such as ‘magnesiuen sulfate and magnesiui nitrate, [0038] The amphoteric hyrocarbon surfactants (Compo= rent C) inelude but are not limited to those Which contain in the same molecule, amino and carboxy, sulfonic, sulfuric ‘ester and the like’ Higher alkyl (Cé-C14) betaines and ‘sulfobetaines ae included. Examples of commercially svail- able products include Chembetaine CAS aod Mirataine CS, both sulfobetaines, MacKam 2CYSF and Deriphat 160C, & C 12 amino-dicarboxylate. These products are excellent foaming agents and help reduce interfacial tension in water solution [0039] Anionic hydrocarbon sutfatants (Component D) Jnchude but are aot limited to alkyl cartoxylates, slfates, sulfonates, and their ethoxylated derivatives. Alkali metal ‘nd ammonium slls may alsa be used. Anionic hydrocarbon ‘urfactans in the C8-C 16, C8-C 12, and 8-C 10 range are particularly useful [0040] The nonionic hydrocarbon surfactants (Component ) help reduce imterfacial tension andl solubilize other com- ponents, especially in hand wate or sea water solutions. Ta sition, they serve to control foam drainage, foam fluidity, and foam expansion. Suitable nonionic surfactants include but ate liited to polyoxcthylene derivatives of alkylphe- nol, linear or branched alcohols, fatty acids, alkylamines, alkylamides, and acetylenic glycols, alkyl glycosides and polylyecosides as described in U.S. Pat. No. 5,207,932 and ‘thers, and block polymers of polyoxyeihylene and polyox- propylene units [0041] Fuoroctemical surfactants (Component F), which ‘may be useful at low levels, age found ia the many AFFE Patents including but no limited to those deseribed in US. Pat, Nos. 5,616,273, 5,218,021; 5,085,786; 4,999,119; 4,472,286; 4120434; 4,060,489, which are here incorpo- rated by reference [0042] Small quantities of fuosochemical surfactant may be acded fo ineresse extinguishing speed and burnback resistance. But in all instances, the total uorochemical surfactant content is limited to Tess than one-half normal Workable levels in the absence of the inventive mater to provide UL 162 Class B fre performance. This means less than about 0.20% Mucrine as Nuorochermical surfactant in & 3% concentrate or less than sbout (006% fluorine at the ‘working siregth. This compares very Iavorably with data of| US. Pal. No. 5,207,932 leading 10 a commercial product ith low end working Muorine content of 0.013% Horne (a 535% reduction in fluorine content). [0043] Foam aids (Component G) are used t0 enhance foam expansion and drain properties, while providing sol- biligation and antifreeze action, Useful solvents are dis- closed in US. Pat. Nos. 5,616,273, 3,457,172; 342,011 and 3,579,446, which are herein incorporated by reference. Jan. 6, 2005 [0048] Typical foam aids are alcohols or ethers such as: cthylene glycol moncalkyl ethers, diethylene glycol ‘monoalky ethers, propylene glycol monoalkyl ethers, dipro- pylene glycol “monoulkyl ethers, wiethylene ” glycol ‘monoalky] ethers, L-butoxyethoxy-2-propanol, glycerine, and hexylene glycol [0045] |The freeze proteetion package (Component H) may Jnclide glycerine, ehylene glycol, diethylene glycol, and propylene glycol. Also included are salts and other solids ‘whieh reduce freeze point such as caleium, potassium, saditum aad ammonium ehlocide and urea. [0046] Component I, the sequestering, buffer, and eorro- sion package, are sequestering and chelating agents exem- plified by polyaminopolyearboxylic acids, ethylenediamine- tetraacetic acid, citric aid, tartaric aid, ntriltracetc aid, bydeoxyethylethylenediaminetriacetc cid and salts thereof [0047] Butlers are exemplified by Soressca's phosphate ‘or Mellvaine’s citrate butlers, Corrosion inhibitors ace only limited by compatibility with other formula componeas, There may be exemplified by ortho-phenylphenol, toluyl azole, and many phosphate ester acids. [0048] Components J is a water soluble polymeric lm ormer and may be wsed forthe formulation of AR (alcohol resistant) agents which ace used to fight bath polar (water soluble) and non-polar solvent and fuel fires. These po ‘meric film formers, dissolved in AR agents, precipitate from solution when the bubbles contact polar solvents and fuel, and foxm a vapor repelling polymer film atthe solvea/foam interface, preventing further foam collapse. Examples of| suitable ‘compounds. include thixoteopic polysaccharide ‘gums as descrined in US. Pat. Nos. 3,957,657; 4,060,132; 4,060,489; 4,306,979; 4,387,032; 4420434, 444,13: 4464267, 5,218,021, and 5,750,043, whieh are herein incorporated by reference, Suitable commercially available compounds are marketed as Rhodopol, Keleo, Keli, Actigum, Cecal-gum, Calaxy, and Kazan, [0049] Gums and resins useful as Component J include acidic gums such as xanthan gum, pectic acid, alginic acid, ‘gir, carrageenan gum, shamsam gum, welan gum, mannan gum, locus bean zum, galactomannan gum, peetn, starch, bacterial alginic avid, succinoglucan, gum arabic, car boxymethyleellulose, heparin, phosphotie acid polyssecha- ride gums, dextran sulfate, dermantan sulfate fucan sulfate, ‘gum karaya, gum tagaeanth and sulfated locust bean gum [0080] Neutral polysaccharides useful as Components J Include: cellulose, hycoxyethyl cellulose, dextran and ‘moslfed dextrans, ocutral glucans, hydroxypropyl celli- lose, as well a6 other cellulose eters and esters. Modified starches include starch esters, eters, oxidized starches, and ‘enzymatically digested starches, [0081] Components K, antimicrobials and preservatives, ‘may be used to prevent biological decomposition of natural product based polymers incorporated as Components J. Included are Kathon CG/ICP and Givgard G-4-40 manus tured by Rohm & Haas Company” and Givaudan, In respectively, as disclosed in U.S. Pat. No. 5,207,932. Addi tional preservatives are disclosed in the above polar agent palenis—US. Pat, Nos. 3:957,657; 4,060,132; 4,060,489; 4306,979; 4,387,032; 4490464; 4.424.133; 4,464,267, 5218021, and 5,750,043, which are herein incorporated by reference,US 2005/0001197 Al [0082] Components L are polymeric foam stabilizers and thickeners which eam be optionally incorporated into AFFE and AR-AFFF agents enhance the foam stability and foam “rainage properties, Examples of polymere stabilizers and thickeners ae partially hydrolyzed protein, starches, poly- vinyl resins such as polyvinyl aleohol, polyaerylamides, carboxyviny! polymers, polypyrotiine, and poly(oxyeth= ylene) lol [0033] Macy commercial synthetic surfactant concen Teale are marketed worldwide by Chemguard, Kidde, and ‘Tyco. The addition of an effectual high MW acide polymer and coordinating salt to these liquid concentrates st an ‘effective concentration may be encompassed by the present Jnvention. These prodvets include: Class A foams (CLASS ‘A PLUS and SILVEX), excelent for extinguishing forest fires, structural fre, and tice fires; High expansion foams sold under the names HEX, EXTRA, C2, and VEE> FOAM, Vapor suppressant foam sold by Chemguard as VRC foam; Bomb foam, « 6% product sold by Chemguard 88 AFC-380. [0084] Synthetic surfactant concentrates listed as “wetting agents” by Underwriters Laboratory are aso included as base surfactant mixtures for use inthis invention, Products listed by UL as “weting agents” includ the following: Fire ke by Biocenter Ine Bio-Fice by Enviroreau Technolo- ies LLC; Enviro-Skin 1% by Environmental Products Ine; F-500 by Hazard Control Technologies Inc; Knockdown by National Foam Ine} Phos-Chek WDSSI by Solutia Toc Flameout by Summit Environmental Corp. Inc. Micro- [Blazeout by Verde Environmental Inc; Bio-sotve by West- ford Chemical Corp. EXAMPLES [0085] In the examples below, references are made 10 Specifications used by te industy to evaluate the efficiency ‘of synthetic surfactant concentrates. More specifically, the ‘examples rele tothe following specications and laboratory test methods: [0086] Sucface Tension and Interfacial Tension: According, fo ASTM D-1331-56, Based on laboratory tests, the surface teasion of eyelohexane used for calculating the SC was 24.7 ddynesiem, [0087] The UL 162 Type IIL, Class B, topside, ire test for AFFE agents was used to test the 3% synthetic liquid ‘concentrates as promixes in tap water and synthetic sea Water For each fre test 55 gallons of heptane was charged to a 50 ft? heavy steel UL pan with enough water in the bottom t give at least eight inches of sideboard. A US military type aspirating nozzle adjusted wo give a 2.0 gallon per minute flow rate was placed on a stand, The fire is lit, allowed to burn for 60 seconds, and then foam is directed ‘onto the surface of the fuel unl the fire i about 75% ‘extinguished, Then a firefighter picks up the nozzle and ‘moves the foam stream back andl forth until 9% extinguish ‘ment (contol time) is obtained at which time the firefighter i allowed to fight the fice from {sides ofthe pan, Times ae recoded a 08% control and at extinguishment. Foam application i continued for a total of 3 minutes [0088] At about 8 minutes, a 1.0 square foot see! stove: Pipe is placed 1.0 ft fom each side of the comer last ‘extinguished and all foam inside the pipe is eemoved, After Jan. 6, 2005 ‘waiting 9 minutes from foam shut-off, the fuel inside the pipe is lit and allowed to bara for I minute. The pipe i thea ‘removed and timing ofthe Burnback started. When the fre increases 10 20% of the pan area, the burnback time is recorded [0059] Foam quality is measured by taking the expansion ratio and drain time from the nozzle after running the fre test [0060] An APFF procuet passes this fire test by extin- ‘ishing before 3 minutes and having & burmback equal to oF {greater than 5 minutes. Stronger precicts give shorter extin- uishing and longer buraback times. [0061] The UL 162 Type II, Class B, topside, fre test for Fuoroprotein (FP) agents was used totes the 3% synthetic liquid concentrates as premixes in tap Water and synthetic sea water For each fre tet, 55 gallons of heptane was charged to 450 f heavy steel UL pan with enough water in the bottom to give a least eight inches of sideboard. AUS rnlitary type aspirating nozzle adjusted to give a 3.0 gallon per minute low rate was placed on stand. The fiteis lit Allowed to bura for 60 seconds, and then foam is directed foto the surface of the fuel until the fire is about 75% extinguished, Then a Mrefigher picks up the nozzle and ‘moves the foam stream back and forth until 90% extinguish- ‘cat (control time) is obtained, at which time the Brefigh js allowed to fight the fire from two sides ofthe pan. Times fate recorded a 90% control sad at extinguishment, Fost pplication is continued for a total of §.0 minutes. [0062] At about 14 minutes, a 1.0 square foot see! stove- Pipe is placed 1.0 ft from each side of the comer lst ‘extinguished and all foam inside the pipe is removed. After ‘waiting 15 minutes fom foam shut-of, the fuel inside the pipe is lit and allowed to bum for 1 minbte. The pipe is then ‘emowved and timing ofthe buraback is started, When the fi increases (© 20% of the pan area, the burnback time is recorded [0083] Foam quality is measured by taking the expansion ratio and drain time from the nozzle after running the fre [0068] _A.FP product passes tis fre test by extinguishing before 5.0 minutes and having a bumnback equal oor greater than 5 minutes. Stronger products give shorter extinguishing and longer burmback limes. It shouldbe noted that FPs when ‘compared with AFFF agents are applied ata rate of 006 vs (0.04 galt and for wo minutes longer than AFF agents; 2 longer buraback of 21 minutes minimum is eequred for FPS versus 15 minutes for AFFP agents [0065] Simple 3% synthetic surfactant concentrates were Tormutated to demonstate the invention; Examples A-H are given below in Table 1-1 to show performance enhancement ‘due to HS-100/Magnesium sulfate interactions [0066] The Chemguard 1IS-100 used as te anionic hydro- ‘achon sucfactant is that manufactured by Chemguard Inc at 445% solids in water, Chembetaine CAS is used a a 50% solids coeoamidopropy! hydroxypropyl sulfobetane, and is available from Chemon, Mackam 2CYSF is 50% solids ‘ety dipropionate from McIntyre while Deriphat D-160C is 20V% solids lauryl dipropionate from Henkel. Sulfochem ADS is 30% solids sodium decyl sulfate in water from Chemron. Sulfochem NOS is 40% solids sodium a-actylUS 2005/0001197 Al ‘sulfate in water from Chemron, Witeolate 7108 is solids ammonium lauryl ether sulfate from Witzo, Magne ‘sium sulfate is charged as the beptabydrate TABLE ta wey bor Fo aye sae ison” Spin aon mo 209 m0 380 mo W950 Srmadag 07 -19 20 1S 19 as -o7 as Jan. 6, 2005 Compaen fein ok rou [0069] ‘TABLE 2 yp Ca He Fe Tes, Pinson obra sens A BC OD OE OF OO ismo@ oa) 18 a7 Ae 30 a8 a0 Mageium 300 310 300 90 300 nd ano $0 sie tate 2 go ® e & © ao : oS Fam SA 61 78 16 80 63 G1 62 fam ao 3333 de Bn Se OSS BS “Tine owner cow soe fom liu as 0 ae a6 ae dad TABLE 2 ‘tama {ULI ys amy apo Fe as, frien Pipe Sas a oat cx Se Nae kK LMS or Berge D0 0 0 0 oo ae Mae Soe a 3 Duwoe Crartine “to Soe ‘09 ‘is “So “as “to “to ea ee ee Sos nt SReetem 20806 6D 075 99m OPK NA 100% 100% am OO mR 2 xaos man soe wees Teneo Bo oo 0 Gn Zo Bo SRG HOG an aim ano sno 80 380 sao Mo soo 0 fo ft ote wo OS {0 (oon) TABLE te TABLE 26 omnes ‘ULI pe Gam Hapa Fn a, cmon ook ss roy tea ae a iw Maem OR 6 oT A eee ‘Sethe cas 09 8 8 og Rr ee ep ete SarUS 2005/0001197 Al ‘TABLE 2e-continued ‘UL 162 Tye Ml, Gas B. Hepa Fe Ts, ven OR ST UO Fame R473 «6S ARTS Tei ies Examples AE [0072] Examples A through E (Fables 1a and 2a) demon~ ‘trate definitive improvement in UL. 162 type performance ‘when the HS-100 content is increased trom 0 1 3.6% while holding the magnesium sulfate content coastant at 30%; all ‘ther formula components are held constant. In fact, Example A without HS-100 did aot eontrl the fie (60% ‘extinguishment at 5.0 minutes) while Example E extin: uished at 4 rapid 1.9 minutes, bad 100% foam cover at burnback time, and had 4.1. minutes burnback; a vast improvement om ineceasing I1S-100 concentration. Cleasy, the performance improved with each inerease in the HS-100 ‘content going from Example A through E wheo the magne ‘sium sulfate content was held at 30%, Since all other ‘components were held constant, the UL. 162 type perfor- ‘mance improvement must be dic to the HS-100; 4 high ‘molecular Weight anionic polymer. [0073] From Examples AE, itean be seen that there is no ‘correlation between the spreading cocllicient (SC) and the fire perlormance of the formulations. Example A with the least negative SC had the poorest perlormance, while Example E had a negative 1.9 SC and performed bes in the series, It can be reasoned that the fie performance is independent of the SC. Therefore, the interaction between the HMWAP and polyvalent salt must stabilize the foam bubble tothe flame and hot fuel rather than enhance the surface active properties. Examples EA and 1,1 [0074] Examples E through H (Tables 1a and 2a) show a ‘dramatic reduction i performance asthe magnesium sulfate ‘content was reduced trom 30% to 5% in increments while holding the HS-100 content at 3.6%. In fact, Example H ‘with only 5% magnesium sulfate snd 3.6% HS-100 (8 high Jevel) would extinguish the fre, but at burmback time only 25% of the pan was covered with foam. Therefore a buraback ‘could not be run. Certainly, UL 162 fire performance ‘decreased with each reduetion in the magnesium sulfate [0075] The SCs of Examples Fl, as above, did not ‘correlate with the fre performance of the formulations. It ‘nist again be concluded thatthe surface active properties do ‘ot contol the fire performance characteristics ofthe work ing invention, Jan. 6, 2005 [0076] Examples 1 and J illustrate two Formulas wilizing Mackim 2CYSE instead of Chembetaine CAS, where Example 1 contains 3.6% HS-100'30% magnesium sulfate and J has Of HS-100/30% magnesium sulfate. As in the ‘examples above (EA), even with s high magnesium sulfate feontent Example J without HS-100 would aot even extin- aguish the fire while Example T performed well, Charly, Song UL.L62 fire performance requires that both HIS-100 And magnesium sulfate be at effective levels [0077] However, various combinations of HS-100 and ‘magnesium sulfate were seen 10 provide enhanced tire performance. Example G with 3.6% HS-100/10% magne- sium sulfate demonstrated approximately equivalent perfor ‘mance to previously. presented Example D with 2.7% S-100/30% magnesium sulfate, Therefore, exeelleat per ormance is obtained from lower HS-100 content formla- sions if higher quaotitis of magnesium sulfate ae used, [0078] _1t should be noted that even at 3.6% HS-1005% ‘magnesium sulfate and 0.9% HS-100/30% magnesium sul- fit, the fies were extinguished at 3.0 and 3.6 minutes; demonsirting the ellectiveness of larger quantities of THS-100 in the presence of low levels of magnesium sulfate or visa versa. Higher quantities of either HS-100 or mag- fesium silfate are reqired for obtaining acceptable bu back performance. Examples K-M (Tables Ib and 26) [0079] Example K is varied from Example E by only replacing Chembetaine CAS with Mackam 2CYSP at 2 higher actives level. I can be seen that Mackam 2CYSE works well a replacement for Chembeiaine CAS since both formulations had excellent extinguishment and burn- back performance. Examples K-M demonstrate the effect of further increasing levels of amphoteric hydrocathon surta fant on UL 162 fie performance. Examples K-M repress «series with increasing levels of Mackum 2CYSF ampho- ‘eric surfactant. The best performance overall was obtained by Example L with 28% Mackam 2CYSE. It should be noted that Example L passed all specifications for the UL. 162 fre test including the burnback which requires mi ‘mum of 5 minutes for the burnback. Examples N-P (Tables Ub and 26) [0080] Examples N and © compare foemulas having i= {erent anionic hyeocarbon surfactants at the same actives content. It canbe seen that 7.5% actives Sulfochem NADS (odium decyl sulfate, Example N) and Witeolate 7103 (ammonium dodecyl or lauryl ether sulfate, Example O) provide equivalent fire performance, Therefore, sodium ‘cyl sulfate andl ammonium dodecyl ether sulfate work to provide similar performance in these formulations. [0081] Example P exemplifies a very different hydroear- bon surfactant mixture with 4.8% actives Deriphat 160, « sodium lauryl sulfate amphoteric, and 2.0% actives Sulfo- chem NOS, sodium octyl sulfate. Although extinguishment was somewhat slower and buraback was shorter than for Examples N&O, good performance was sill obtained for suet a Targe change inthe base formula when the HIS-100 and magnesium sulfate contents were 36% and 30%, respectively Examples Q-S¢Tables Le and 2c) [0082] Examples A-P refer to UL fire tests based om the Fuoroprotein (FP) fre test procedure wit foam applied atUS 2005/0001197 Al 3 gpm (0.06 gal?) for 5 minutes. Examples Q-U were tested using the AFFF tes regime of 2 gpm (0.04 gait) for 3 minutes; a tougher lest procedure since oaly 6 gallons of premix is used versus 15 gallons forthe FP test. Examples 5 exemplify the importance of HS-100 and magnesium ‘sulfate for obtaining AFTF iype UL 162 fie performance. AS S100 is reduced from 2.3% (Ex. Q), o 1.4% (Ex. R) and finally 0% TIS-100 (Ex. 8), the performance went from ‘excelent, to moderate, 1 poor. Example Q, however, was a ‘trong proiuct mecting all UL. 162 fire performance require iments. Even at 39% less HS-100 content, Example R ‘extinguished the fire at 2.5 minutes and gave 1.9 minutes of bumback time, Only at 0% HS-100 did fire performance properties disappear. [0083] 1 should be further noted that for Examples QS, ‘no solvent was included in the formulation to enhance of stabilize foam, yet excellent foam quality was produced, ‘Therefore, itis clear that these formulations do aot requite the ation of solvent foam boosters, Examples TEV (Tables Le and 2 [0084] Examples T&U are similar to Example Q, but have the addition ofa solvent foam slabilizer, hexylene glyecl, and have varied levels of Mackam 2CYSF and Sulfochem NADS, Examples T&U ean be seen in Table 2c to provide ‘exceptional extinguishment at only 1.8 minutes and burm= buck times prester than 8 0 minvtcs with tap water. Example U whem tested with sea water gave an extinguishment of 2.3 minutes and 6.8 minutes for burmback; still excellent per formance [0085] Example V demonsisates excellent performance in ‘sea water without the use ofa foam stabilizer and with only 15% magnesium sulfate. Extinguishment was less than 2 minutes and burmback time was greater than 8.0 minutes. [0086] These examples demonstrate thatthe combination ‘of a HMWAP and a polyvalent salt provides UL. 162 Class B fire performance using either the AFFF or FP standard ‘conditions, [0087] The UL 162 Type I, Cass B fice test reeognizes 8 diferace between AFFF and FP type fre extinguishing gens. AFFP agents must extinguish in 3.0 minutes ot ess ‘an application density of only 004 gall while FP gents ‘only need 0 extinguish in 5.0 minutes at an application ‘ensiy of 0.05 galt, This means 6.0 gallons of peemix are used for AFFF while 150 gallons of premix are applied for TP agems. As noted shove, however the humback equ ments for FP agen are meve severe than for AFFF agents TP agents must have a minimum of 21 mutes bueback from ime of fam shutoff compared to 15 minutes inimam bumnbaek for AFFE agents [0088] The fre fighting compositions, as described herein, may be applied to noa-polar liquid hydrocarbons to extin- suish or retard fre from sueh liquids during burning. The ‘composition may be applied both to the surface of such liquids or may be introduced below the surface, such as through injection. The composition may be applied in com bination with other firefighting agents If necessary such as the disl-sgent application of both foam ane a dry chemical ‘or powder fire fighting agents. An example of such ad ‘chemical or powder agent is that avilable commercially as Purple K. In such dual application, the fre fighting azents Jan. 6, 2005 ay be applied through the use of adjacent or as generally concentric nozzles. In some instances, the dey or powder ‘agent may be applied alone to intially extinguish any fame, ‘with the foam being applied to preveatreigiting ofthe Cue. [0089] While the invention bas boen shown in only some of is forms, it should be apparent to those skilled inthe that it isnot so limited, but is susceptible to various changes. and modifications without departing from the scape of the invention. Accordingly, itis appropriate that the appended claims be construed broadly and in a manner coosistet with the scope of the invention. 1 claim 1. A foam concentrate comprising water and a high polecular weight acidic polymer (HMWAP) and a coord rating salt, the foun concentrate providing fire-fighting ‘composition when mixed wit water so tht the fire-fighting ‘composition does nol form a stable seal on cyclohexane and ‘meets UL 162, Clas B performance eriteria for at least one ‘of AFFP agents and fluoroprotein (FP) agents without requiring organic fluorine 2. The foam concentrate of elaim 1, futher comprising: at leat one of a fuorochemical surfactant, an amphoteric hydrocarbon surfactant, an anionie surfactant, 2 n0n- jonie sucfactan, a foaming aid, « freeze protection agent, a sequestering agent, a buffering agent, a como- sion inhibitor, « polymeric film former, an antimiero- Dial agent, a preservative, a polymetie foam stabilizer and a polymerie foam thickener 3. The foam concentrate of claim 1, wherein the fie fighting composition meets UL 162, Class B. performance criteria for both AFFF agents snd luoro- protein (FP) agents without requiring organie fluorine 4. The foam concentrate of elsim 1, wherein: the foam concentrate has a HMWAP cootent that provides, ihe fite fighting composition with from about 0.0L t0 about 0.3% HMWAP by weight of the fre fighting ‘composition ‘5. The foam concentrate of claim 1, wherein: the foam concentrate hss 8 coordinating salt content that ‘provides the fie fighting composition with from about 0.110 about 1.5% ofthe coordinating st by weight of the fre fighting composition. 6. The foam concentrate of elaim 1, further comprises 3 ‘uorochemicalsuefactant, and wherein the foam concentrate thas a uosine content provide from the fuorochemical that provides the fie fighting composition with less than about 0.006% forine by weight of the fre fighting composition 7. The foam conoenttate of claim 1, wherein the foam ‘concentrate is used in an amount of from about | to about 10 paris concentrate to about 9010 about 99 parts water to form the firefighting composition, '8. The foam concentrate of claim 1, wherein the foam concentrate has 2 Muorine content that provides the fre fighting composition with less than about 0.002% fluorine by weight of the fre fightin composition. 9. The foam concentrate of claim 1, wherein the foam concentrate has 2 Muorine content that provides the fre Fighting composition with less than about OKI fluorine by weight of the fre fightin composition.US 2005/0001197 Al 10, The foam concentrate of claim 1, wherein the fre fighting composition bas a spreading coellicient agains! ‘eyelobexane of zero or less. IL. The foam concentrate of claim 1, wherein the foam ‘concentrate has a HMWAP content that provides tho fice fighting composition with from about 0.03 10 about 0.2% HMWAP by weight of the fire fighting composition, and ‘wherein the foam concentrate has a coordinating salt content tat provides the fire fighting composition with trom about (0.12 ta about 1.2% of the coordinating salt by weight ofthe fire fighting composition. 12, The foam conocntrate of claim 1, wherein the coor inating salt includes those selected from salts and elecito- Jytes of aluminum, antimony, barium, boron, calcium, eop- Pe, toa, magnesivm,calciom, strontium and zinc 13. The foam concentrate of claim 1, wherein the HMIWAP includes those polymers having C4 to C22 alkyl branching and having an average MW of from 5000 or rear 14. A fire ighting composition comprising water, «high ‘molecular weight eedie polymer (HMWAP) and a co nating sll the fire fighting composition meeting UL. 162, (Class B petformanec criteria fora least one of AFFF agents and fluoroprotein (FP) agents without requiring organic ‘Buorine and that does aot form a stable sea on eyelohexane. 18, The fire fighting composition of claim 14, further ‘comprising: at least one of «uorochemicalsuefactsat, an amphoteric hhydrocarbon surfactant, an anioaie surfactant, a pon fonic surfactant, a foaming aid, a freeze protection agent, sequestering agen, buffering agent, a eorro- Jan. 6, 2005 ion inhibitor, a polymeric flm former, an aotimicro- bial agent, a preservative, a polymeric foam stabilizer and a polymeric foam thickener, 16, The firefighting composition of claim 14, wherein the fie fighting composition meets UL 162, Class B. performance criteria for both AFFF agents and fluoro Protein (FP) agents without requiring onganie fuocne. 17. The fre ghting composition of claim 14, wherein the HMWAP content is from about QOL © about 03% by ‘weight of the firefighting composition, and wherein the coordinating salt eontent is from about (1.1 about 1.5% by ‘weight ofthe fie fighting composition. 18, A method of extinguishing or retarding a fire com- prising: providing a ie fighting composition comprising water, high molecular weight acide polymer (HMWAD) and 8 coordinating salt he ire fighting composition meet- ing UL 162, Class B performance evteria for atleast ‘one of AFFF agents and flioroprotein (FP) agents ‘without requiring organie fluorine and that does not form a stable seal on cyclohexane; and applying the composition to an area where extinguish: mentor retardation of the fre is desired. 19. The method of claim 18, further comprising: applying the composition othe area in combination with ‘dey fie fighting ageat