us United States cz) Patent Application Publication co) Pub. No.: US 2013/0277597 Al oy 03) om en @) (66) (6) Bowen et al. AQUEOUS FIRE-FIGHTING REDUCED FLUORINE CONTENT Inventors: Martina E, Yuan Nie, Marinette, WI (U owen, Marinette, WI (US) Pamela U! AMS WITH A. Havelka-Rivard, Wallace, MI (US) Assignee: Tyco Fire Produets LP. La ws) Appl.Noz 13876,460 PCT Filed: Oet.3, 2011 PCTNo: — PETUSIUISS628 $371 M0), (2),(4)Date: Jun. 28,2013 Related US. Application Provisional application No, 61/389.0 1.2010, rata andale, PA filed on Oct IAL S 2013027759) (43) Pub, Date Oct. 24, 2013 ication Classification (1) Ince ABD 102 2006.01) @) v. cee 62D 1/85 (2013.01) USPC 252/3,252/8.05 6 ABSTRACT Aquoous fil forming firefighting composition concentrates ‘areprovided that contain an effective amoual of monomilic ‘witeronic or anionieC, peritoroalky] surfactant having a ‘molecule weight les than $00 daltons, The compositions also contain an effective amount ofa foam stabilizing agent, and fanellective amount of at least one non-lvorinated surfactant. The composition has less than 0.8% F, and is substantially free of any surfactant containing a periuoroalky] group con- taining more than 6 carbon atoms. The composition meets Military Speciticaton MIL-F-24385PUS 2013/0277597 Al AQUEOUS FIRE-FIGHTING FOAMS WITH REDUCED FLUORINE CONTENT PRIORITY DATA AND INCORPORATION BY REFERENCE [0001] This international application claims the benefit of priarity to U.S. Provisional Patent Application No. 1/389, (027, filed Oct. 1, 2010, entitled “Aqueous Fire-Fighting Foams With Reduced Fivorine Content” the contents of ‘which is hereby incorporated by reference in is entirety. BACKGROUND 0002} Firefighting foam concentrates contain mixtures of surfactants that aet ws fouming agents, together with solvents and other additives that provide the desired mechanical and ‘chemical propectes for the foam, The concentrates are mixed ‘with water i stu and foamed by mechanical means, and the resulting foam is projected onto the fire, typically onto the surface of @ burning liguid. The concentrates are typically ‘used at a concentetion of about 1-6, [0003] Aqueous film-forming foam (AFFF) concentrates fre designed to spread an aqueous film on the surfoce of hydrocarbon liquids, which increases the rateat which the fre ‘can be extinguished. This spreading property is made pos sible by the use of perluoroalky| surfactants in AFF, whieh produce very low surface tension values in solution (15-20 ‘dynes em), thereby” pemitting the aqueous solution 10 spread on the surface ofthe hydrocarbon liquids. 0004} "However, typical AFFF foams are not effective on fires caused by water-miscible fuels, suchas low molecular ‘weight loohols, ketones, and esters andthe like, because the miscbilty ofthe solvent leads to dissolution and destruti ‘ofthe foam bythe fue. To-addres ths ise, alcohol resistant AFFF (ARAFFF) concentrates are used, which contain & ‘water-soluble polymer that precipitates on contact with a ‘water-miscible fuel, erating a protective layer between the fel and the foam. Typical water-soluble polymers sed in ARAFFP are polysaccharides, suchas xanthan gums. ARAFFF foamsarecffetiveon both hydrocerhon and water- soluble fuels [0005] | Conventional AFFF concentrates contain mixtures ‘of perflioroalky! and non-fuorinated surfactants, each of ‘which may be anionic, cation, nonionie of amphoteric, sol vents such as glyeols andior glyeol ethers, and minor addi tives such as chelating agents, pH buffers, corosion inhi torsand the ike. Various AFFE concentrates are deseribed in, orexample, US. Pt, Nos. 3,047,619: 3,257.407: 3,258,423; 3.562186: 3,621,050; 3,655,555, 3,661,776, 3.677.347 3.750,981; 3,772,199, 3.789.265, 3.828085, 3.839.425; 3840318 3.941.708; 3.98075, 3.987.657: 357.658: 3,963,776: 4.038.198; 4,042,522; 4,049,556; $060,132; 4.060.489: 4,059,158; 4,000,976, 4,099,574; 4,149,599; 4,203,850; and 4200407, ARAFFF concentrates are described i, for example, U.S. Pat.No. 4.060.489: US. Pat No. 4,149,599 and US. Pat. No. 4.387.082. BRIEF SUMMARY {0006} Aqueous lm forming firefighting composition con- ‘entrates are provided that contain an effective amount ofa Perituoroalky! surfactant, an effective amount ofa foam sta- bilizing agent, and an effective amount of atleast one n0n- ‘Tvorinated surfactant. The perfiuorcalkyl surfactant is ‘monomeric zwitterionic or anion C, peeluoroalkyl surfae- Oct. 24, 2013 ‘ant having a molecule weight less than 800 daltons. The composition has ess than 0.8% F, and is substantially free of ‘any surfactant containing a perftuoroalkyl group containing ‘more than 6 carbon atoms. The composition meets Miliary Spocitication MIL-F-24385F, [0007] The perftuoroalkyl surfactant may have a structure represented bythe formal : {0008} where 10009] Ris. C, seagbt or branche cain perv all {0010} XisaC.-C,.staightor ranchadchanatkylene, ‘oa C.-C, sight or branched chain alkenslene eon: taining | oF 2 alkene moieties WOU Ys —S—CH.CHERYCONR?)— —0-CH,CH,-N(RYKR?)—, —O—CH,CHOR, CHANIA) 5 OCH CHORIC,S— S--CH,CHORCH,-NOVIR)— o S—CHACHOR CHS [0012] Lis CC, straight or branched chain alkylene, ‘where one carbon ‘atom in the chain optionally may be replaced by —N(RE}R"}— and [013] |Z is —050,",— $0", or COs, [0014] where RR? R°,R*,R° and’ independently may bellorstaightorbranchetchainC-C,alkyland R® may be Hor straight or branched chain C,-C. alkyl or tralkyls Advantagsously, the composition does not contin an ee- ‘ive amount ofa perfivornated surfectant that does not eon- formto formula, although in eran embodiment, thecom- position may contain an effective amount of a fluorinated qoam stabilizing agent containing 3107 peruorintedcarbon atoms [0013] Inspecificemestiments ofthe composition, ¥ may be —S—CHC(RNCONIR?)—, for example where R may be 1 or strait chain alkyd and R may be 1. In furher embodiments, Y_may_ be: —O—CH,CH, N(R") ‘where for example, Rand Rare Hor eth In stil further embodiments, Y may be —O-CH,CH(OR')CH, NUR) (R})— where, for example, R° and may be H or meth, and R® may be Hortrialkyliyl. In yet more emboetiments,¥ nay be —O-—CH,CIOR)CH,—S—, where, forexampie, may be Hor ialkyily. nother embodiments, ¥ may be S—CH,CHOR' CH: NVR), where, for example; Rand R*may be Hor methyl, and R° may'be Hor ‘wiakkybilyl, In sll other embodiments, Y may be S—CH,CHOR')CH,-S—, where R? may be Hort alkyl 10016) In any of these embodiments, more than one per= Myoroalkyl surfactants of formula Tmay be wed [0017] In particular emostiments of the concentrate the ‘on-fiuorinaed surfactant may bean anionic surfactant and! forthe foam stabilizing agent may be a plyeo eer In addi tion the composition may contain a corrosion inhibitor. [0018] In any of these embodiments, the composition may also contain an alkylpolyglyeoside, typically nan amount of about 03 to about 7%. In farther embodiments, the compo- sition may also contain polysaecharide gum, typically nan amount of about 0.1 to about 3% [0019] Ina spovfic embodiment of the composition, the oam stabilizing agent is present in an amount of 1-50%, the ‘on-fuorinated surfactant is present in an amount of 0.1 to 30% and the peuoroaky! surfactant or mixture of surse- ‘ants of formula Tis present in an amount of 0 toUS 2013/0277597 Al 10020] Also provided are fire-fighting Foams, containing @ ‘composition as described above, and water oF an aqueous Tiguid. In specific embodiments, the aqueous liguid may be brackish water or seater. 10021] The compositions as deseribed above may be used Jn methods of making a firefighting foam, where the com- position is foamed with water oran aqueous liquid. In specific ‘embodiments, the aqueous liquid may be brackish water seawater DETAILED DESCRIPTION 10022} Until recently, aqueous film forming foams that were used for fire fighting invariably contained surfsctants having perfluoroalky chains where the perlluroalkyl group was at least a perfluorooety! group. It was believed that & surfactant required atleast a perfluorooes] moiety to provide the necessary physicochemical attributes for efficient and persistent foam formation for firefighting applications. See 'WO03/049813 However, perluorovety] moieties have been shown to be environmentally persistent and to aecumlate i the vers of est animals, leading o cals forthe phase-out ol materials containing a perfluorooctyl group. Recent regul- tory efforts suc asthe United States BPA Stewardship Pro- gram and EC directives pertaining to telomere-based higher homologue perftorinatet surfactants have sought to diseour- ‘age use of perfluorooetyl-containing surfactants n response, ‘various surfactants have been developed containing perBio- rohexyl (commonly refered to as "Ct 5.688.884. [0023] Although C6 fheorosurfactats have been reported to he satisfactory for less demanding applications, sue as ‘leaning solutions, the reduction in engi ofthe perlaono= alkyl chain unfortunately leads ta decrease in the ability (0 orm long lasting persistent foams withthe propertis acces- sary for elfectve fie ighting. Thus, AFFF and ARFFF con- ‘entrates where the perluoroocty! surfactant is replaced by ‘an equivalent C6 compound are unable to meet the require rents ofthe US and intemational standards for fire fighting applications 10024] To counter this loss oF activity, manufacturers have been forced to inerease the concentration of urosurfactant in AFFF concentrates andior to use oligomeric surfaetants ia ‘hich mulkipleperfaoroalkyl groups are covalently attached to shor polymeric carrier molecules, See WO01/030873. In both instances the total eoncentration of faorine atoms (cl- ‘ulated on a weight percentage basis) remains at an undesir- ably high level. 10025] Unfortunately, until the present time it has not been possible to prepare compositions containing perhuoroalky _Eroups that are shorter than perfluorooety! yt stil retain the necessary properties o allow preparation of elective AFFF at the indstral standard” of fluorine levels. Unexpectedly, it has now been found that certain fuorostefactans containing (C, perfluora moicties ean be prepared that can be used to replace C, pertluero moieties in allowing the preparation of AFFF. Moreover, even more unexpectedly, these luorosur- Tactants ean be used (0 prepare AFFF concentrates that are sill effective even when foamed with water containing a high salt content, eg, seawater or brackish water 10026] The C, Muorosurfaetants that provide these highly desirable and heretofore unattainable properties are mono meric, whieh in the present context shall be understood £0 Oct. 24, 2013 seferto molecules havinga single clearly defined structure, as ‘opposed to multimeric surfactant compositions were AMuoroalkyl-containing moieties are covalently Tinked 10 ol gomerie or polymeric easier molecules, Suck multimeric ‘compositions contain surfactants with a range of molecular ‘Weights ad a corresponding variety of molecular stevtures ‘and compesitons. Moreover, most conventional perfinoro- surfactants contain mixtures of different chain lengths (7 cally Cay Cay Cay Cy ete) a a reslt of the telomerization process used in thelr preparation. The present monomeric uorinated surfactants are essentially fe of pefluoroalky] groups of other chain lengths. Thus, for example, aC, mono- ‘meric surlactant is essentially free of Cy, Cy, Car Cx, Cos [0027] Tae monomeric Cy Auorosurfactants advant steously fave a molecular weight of fess than 800 Daltons, ‘which further distinguishes them from the multimeric com positions deseribed above. Moreover, when the monomeric (Cy Muorosurfctanis ae formulated with an effective amount ‘ofa foam stabilizing agen, forexample,aglycot ether andan effective amount ofa non-fuorinated surfactant, the resulting {cancentetes moet the stringent requirements of US Military Specification MIL-F-2438F for ie fighting at concent sion where the final concentration of fluorine atoms on @ level of per ormance at low uorine levels is unprecedented and can be achieved witha composition that is substantially Tree of ny ‘Tuorosurfactant containing perflaorooety (or longer chains Inthe present context composition is substantially fre of a ‘comportent wien that component is present, it alla trace CGompurty) levels that are too low to materially affect the properties ofthe composition. The C, Suorosurfctants can be zwitterionic or anionic. [028] The monomeric C, Auorosurfictants can be repre- sented by the Formal Re X¥LZ, 1 (0029) Where [0030] "Ris a Cs straight or branched chain perfor alkyl. X isaCs-, straight or branched chai alkylene, ‘ora CC, sight or branched chain alkenslene con- taining 1 OF 2 alkene moieties, Wot] Ys S$ —CHACIKR CONGR —0-CH,CH,-N(RYWR?)—; —O—CH,CHOR, CHAN) 5 O—CHCHOR VCH S—; S—CH,CHOR ICH, -NRIR) on —S—CH,CHOR ICH, —S— (0032] Lis C.-C straight oF branched chain alkylene ‘where one carbon atom in the chain optionally may be replaced by —N(RR”}—s and [0033] Zs —0S0,-, $04", or —CO~. [0034] Inthe compounds of Formula each R',R2,R0,R*, RY of R” independeutly may be Hor staight or branched hain Cy-C, alkyl, and R? may be H or straight o branched chain Cy-C, alkyl or talks [0035] "AS used herein the term “alkyl group” or “alkyl” includes straight and branched carbon chain radicals. The term “alkylene” relers to a ciradical of an unsubstituted oF substitute allane. For example, Cy alk isan alkyl oop having from | to 6 carbon atoms. Examples of Cy-C, Sraght-chain alkyl groups infude, but are not limited ty methyl, ey n-propyl, n-butyl, aspentyl, and a-hexyl Examples of branched-chain alk groups include, but are not Timited to, isopropyl, tert-butyl, isobutyl, ete. Examples ofUS 2013/0277597 Al alkylene groups inelude, but are not limited to, —CH, “CH,—CH,,—CH,-CH(CH,) CH, — and (CH) sy AIkyI groups éan be substituted or unsubstituted, as indi- ‘ated, Examples of substituted ally] include ball, thio alkyl, aminoslkyl, and the like, Alkylene groups can be substiuted or unsubstituted, as indicated. 10036) | Certain compounds as described hercin may exist in multiple erystaline or amorphous forms (i.e. 3s polymor ph). In general ll physical forms are equivalent forthe uses ‘Sontemplated herein and are intended to be within the scope ‘ofthe compositions and methods present described herein. 10037] 1c will be apparent to one skilled in the art that certain compounds as described herein may also exist in tautomeric forms, and all such tautomeric forms of the com- pounds are within the scope ofthe compositions deseribed herein. Similarly, to the extent that compounds deseribed herein contain asymmetric carhon atoms (optical centers) oF ‘double bonds; the racemates, diastereomers, geometric is0- ‘mers and individual isomers (eg. separate enantiomers) are ‘ll ntended to be encompassed within the scope ofthe com: pounds. MG (Cue —GCHRICONT) (ets (Gimcay_ cx, MeFy Cece —0-C1I NR (Clay a c-ci, Oct. 24, 2013 10038] I spevtic embodiments of the epmpound of For ula IY may be —S—CHC(R}}CON{RE)— for example ‘where R may be H or straight chain alkyl and it? may be. Y may also be —O—CHCH, N(R YR?) — where, for cxampl, and Rare Hormetiy|. [nother embodiments. Y may be —Q—CH,CHOOR "CH, N(RYR")— where, for example, R” and R® may be Hor methyl and R° may'be Hor ‘lkysy. Instill other embodiments, Y_may_be —0~CH,CH(OR')CH,—S—, where forexample, R may be H or talkyly. In further embodiments, Y may be SS CHCHOR ACH NOC VRE}— wheres for cxample, Rand R*may be Hor methyl, and R° may be Hor ‘wakkyhilyl, In sGll other embodiments, Y may be ~S—CH.CHOR}CHS—, where R? may be H oF t- alkyl [0039]. ‘The skilled anisan will recognize that the desrip- ‘ionof the surfetantsby the formula -X—YeL.~Z inches cach of the possible combinations of Ry—X—VeL-Z. as ‘ough st forth separately; taking into aceount the valencies of each atom, unless olberwise specifically described. For example, te surlactant include compounds with the follow: ing combinations of elements met (Thy ot —0-cH,HHOR? CH, NVR (Cth (cima, MCF Cage —0-cH,CHORICH,S——— (Clg Cac ci, Meds (Cbuoe 'S-CILCHORSCH,-NOPAR!)— (Ch MCF, (Cope S-CHCHOR CHS Clb (cimcay_ cx, MeFy Cece S-CICHRNCONR)— (Clas Caen ci MCF, (Cope —0- CHIN Cla (cima cx, Clic —c8,— = MCF, Chee 0-CHCHORCHy-S (cli $0, MCF, (Cope S-CHCHOR EH NHR (Clbhs 80, icimcmy_ cH, MGs lager S-CLCHOR KS (Clg 80, acct BCs (lyst S—caLcHR CON) (clans co, MF Cyor 0-08.61 NRYR (cons co, “cic co MCF Ceo 0-CHCHORICHy-NRIR'— (CH co, S(Gimcan cH Meds (Cyr 0-CHeHOR CHS (cons co; icc, mG (Clot S-CaLcHHOR CI NOP AR')— CL) co; icin ci Bey (Aayot Scien ow cu, (cons co, “clic —c1— MF yet S-CHCHORCONI?) (CH sNROIRT) CHa 080, “cic c— MEd (Coy oe Cie cn,— MEd (Cbyoe gic —ci— mG (Clyor MF Cyor cmc bbe 8. NR (CH) NIORTAI), 0805 CHACHOR ICH, NOUR (CH) NIRART) CH), 0805 cucwowscx,s (CH) NBHARTACHLI.y O80 CHLCHOREH, NWR) (CHL sNIRONRT) ACILy —080yUS 2013/0277597 Al sont iin Ce, NOT Geen Ht Cl cen eon — wis pan one Naren Geen. _ 0-cH.cHOR EH _NEIE NGF iy CHap or 7 _09-cH,CHIOR CH,—S— ‘onc. _ i 163) Che —sc.cn0%%e ‘enc. cay Cope 9 encom cont Geen sc Cher oc Nw enon 26s Co excHonen, s Ve onc a — iy aa Fy, HOW 08 Scien [0040] Specific examples of compounds of Formula T ‘include, but are not limited to compounds (a) « 0 on 0 Oct. 24, 2013 4 (CNR Ay OO (Ci) NRORDCIHN 805 (Cio NRORDACIN 805 (Ci) NORD CII» 805 (Cp sNRORTACIIg 805 (Ci NORD) 805 (Cio ysNRORT ACH, 805 (Cig MRR —C0s (Cp NRORD Chg —C04 (Cl NRSYRI} Cy, —C0, (Cg NRORD Clings —C05 (Cy NROYRI} Cy, —C0, (Cg ROR Clings —C0, continued PSN ASO - ou SIMA, yO ou | on ° " Koch cn o on 2 V _ OA [0041] Theskilledarisan will recognize thot more than one perfluoralkl surfactant of formula T may be used when preparing the AFFF concentrate. Typically the surfactant oF ‘ixtareof surfactants of formla Tis present inan amount of bout 0.8% to abort 20% by weight. [0042] In particular embodiments of the concentrate the ‘on-fvorinated surftetant may bean anionic surfactant. Sui able anionic suructans inchide compounds well known ia the at, for example: medium to long chain alkyl sulfites, alkyl ether sulfates, alkyl sulfonates, fatty acid salts sue dey] sulfate, aky! phosphates and the like. 0043} The composition also may coatsin one or more Toam stabilizing agents, Such agents are well known in the att And include glyco ethers, including diethylene glycol ethers (atbitas), such as butyl éarbitol, The foam stabilizing agent js present in an amount of about 1% to about 50%. [0044] Tae composition also may contain one oF more cor- ‘sion inhibitors that minimize corrosion in stomge vessels piping in which the concentrates might be stored overUS 2013/0277597 Al ‘extended periods, Suitable cormsion inhibitors are well known inthe rt, and include compounds such as tolytriaz~ ‘ole. The corrosion iniitor typically is present atthe mini ‘iim concentration (~ about 0-29) required to iaibit cor rosion to the desired extent, although higher concentrations ‘ean be used, [0045] |The composition may also contain an alkypolygly- ‘coside surfactant. Suitable alkylpoly glycosides inhi those ‘described in US, Pat, No, 4,999,119, which is hereby incor Porated by reference in its emtiney. The alkylpolyglyeoside ‘ypically is presenti an amount of about 03 to about 7%, [0046] The composition advantageously contains a high ‘molecular weight Water-soluble polymer, such asa polysae- ‘charide gum, Whenan FFF containing sucha gum sapplied toafirefuled by shydrophilie Figuid, the gum precipitates ‘contact withthe hydrophilic liquid and forms a protective layer, known as a gelatinous mat, which impedes the break ‘down ofthe foam. The gum typically is present in an amount ‘oF about 01 to about 3% [0047] Ina specific embodiment ofthe composition, the ‘oar stabilizing agent is present in an amount of 1-S0%, the non-fvorinated surfactant is present in an amount of 0.1 t0 30% andthe perfluooally! surfactant or mixture of surfae- tants of formula Ts present in an amount of 05 to 2086. 10048] _ Also provided are fire-fighting foams, containing 2 ‘composition as deseribed abave, and an aqueous liquid. TYP cally theaqucous liquids wate In spocific embodiments, the ‘aqueous liquid may be brackish water or seawater 10049] The compositions as deseribed above may be used Jn methods of making a frfghting foam, where the com- positon is foamed with an aqueous liquid, forexample water Inspecitie embodiments, the aqueous liquid may be brackish 10050] Preperation of Molecules of Formula I [0081] The molecules of Formula 1 can be prepared by ‘methods tha are well known in the art. For example, com- pounds such as (a) and (5) (compounds whereY in Formula T fs —S— CHCHIRCON(R?)—) that contain an amide bearing a luorocarbon-containing thioether substituted atthe 5 position may readily be prepared by Michae! addition ofthe thiol wa suitable acrylamide, The acrylamide precursor may be prepared by nucleophile ring opening ofa sultone. Meth- ‘ds of preparing such molecules are described in inter ali, US. Pat, No. 4,098,811, Suitable reaction schemes for pre paring compounds (a) and (b) ro: Oct. 24, 2013 AA: [0052] Compounds such s(e)(2)where the peruor0 moi- cy is appended toa double bond may convenienly be pre- pated using an addtion-limination of a peraoroalky indie {oan unsaturated compound using a radical initiator sich as Rongalite (HOCH,SO;Na), as illustrated. schematially below: BAe PR yw MM ALAA, /\ aUS 2013/0277597 Al Oct. 24, 2013 6 continued Mes Mes a \/ a \/ NO a OO 9 on A ws Ss0,n0 ee fem aaa Sem] » AS ory ek | | arene p : yon Ye —~ - ee | unr acd — wens Ne |US 2013/0277597 Al Oct. 24, 2013 continued eh, — ak ot on | Vv werk. O- AAD NU» (tm wah) ° [0053] Molecules such as (g)-{j) may also be prepared by —_remixture (or “premix” of the concentrate diluted with water, Iicleophilie ring opening reactions of epoxides with, for ‘example, thiols or amines, to produce hydroxyl compounds that can he Further elaborated sing methods tht are well known inthe ar. 10054) | Advantapeously, the composition does not conta an effective amount of perflvorinated surfactant that dacs not conform to formula I, although in eertain embodiments, the composition may contain an effective amount of a fuor= nated foam stabilizing agent containing 3t0 7 perluorinated carn atoms 10085] Specific details of exemplary methods of preparing these compounds ae provided inthe Examples below. 10086] Preperation und Use of AFEF Concentrates [0087] |The components ised above were mixed to prepare an aqueous film forming foam concentrate. This concentrate may then be mixed with water, ypically asa 3% solution, and foamed using foaming devices well kon in the at [0088] |The concentrate, upon dilution with water and aem- tion, produces an aqueous film-forming foam which is applic to body of flammable lig such as a spill or pool ‘which isbuming or subjecttojgnition. The foam extinguishes theburming liquid, and prevents furlier ignition by providing ‘a blanket to cover the fel surface and excluding aie. Film: Torming foam compositions such as those described herein ‘are particularly desirable for extinguishing fires involving flammable fuels, such as gasoline, naphtha, diesel oils hydraulic uid, petroleum and other hydrocarbons, and also may he used for extinguishing fires involving polar solvent {including acetone, ethana, and the like) by addition of suit- able high molecular polymers such as xanthan gums, as ‘described above and also as described in U.S. Pat. Nos. 4,536, 208 and 5.218.021 10059] The concenteates which when diluted with water tnd aersted produce a low density airfoasn which quickly spreads onthe surface ofa body of hydrocarbon fuel, or other flammable liquid forming blanket over the faclorliguid. As the foam (on the surface ofthe Namble liquid) drains, @ ‘mis formed which, ifdisturbed or broken, tends wo reform to seal off hot vapor emanating from the flammable fiquid, thusextinguishing the fire. Although hydrocarbon surfactants ‘may form a foam blanket, te flammable iquid vapors may ‘wick though the foam and reignite. Foams comprising Buo- rosurfactants reduce the ability ofthe flammable liquid from ‘wicking through the film and thereby prevent reigition, [0060] As water under pressure passes through a fire hose ‘ypieally 3 percent by voltme ofthe concentrate composition Js inducted into the hose line by the Venturi effect form a ‘The premix becomes aerated to produce a foam by’ use of an airaspirating nozzle located atthe outlet end of the hose. [Equipment which ean be wscd to produce and apply these aqneaus ait-foams are known inthe att and also are described in publication by the National Fire Protection Association [0061] Preferably, the compositions are introduced into Tire of fame ina amount suffciet to extinguish the Fire oF ‘lame. One skilled in the art wil recognize thatthe amount of extinguishing composition needed to extinguish a particular hhazard will depend upon the nature and extent of the hazard [0062] ‘The following examples are offered to illustrate, but ‘otto limit, the claimed invention, EXAMPLES Example 1 A, Preparation of 3-(methaerylamido)propyl ‘dimethyl betaine {0063} , snr oT ON my “G [0064] Toa 2 of ound bottom flask was added 258 (1.50 vol) of N{3-(dimethylamino}propyi-methaerylamide (AL rich, 99%), 190 g (1.60 mol) of sodium chloroacetate, 1200 8 ‘ofethanol and 60 gof water. The reaetion mixture was stirred under reflux for 2 days, during which a solution of 3 g of ‘NaOIt in 6ml of water was added periodically to maintain the pH of the reaction solution around 8-9, When reaction was complete, the NaCl formed during the reaction was substan- tally removed by filtering the reaction mixture at 0-70 C The filtrate was evaporated to dryness and the erude productUS 2013/0277597 Al was used directly in the next eaetion step without further Puriication, assuming that reaction had gone to completion. 3-{{T-ox0-2-methyl3-[(3.3.4.4 ‘eidecaluorooety! thio propyl |amino}-1-propanium, ‘inner salt 10065) But sti rT — 10066] To.a2L-ofround bottom ask was added 308 g(1.35 ‘mo)) of 34methaerylamidoypropyl dimethyl betaine, 490 g (1.29 mo) of 1H,1H,2H,2H-perfluorooetane thiol, 1000 g oF 1,0 and 250 g of bury! earbtol.~1.0 gof NaOH were added to adjust the pH ofthe reaction solution to 8~9. The mixture ‘a sted at 80-85 C for 14-16 hours until al of the thiol Was consumed, The clear reaction solution was cooled to room temperature to gave 2100 gof sofution containing 1532 ‘wt % of Fluorine, 12 wt % of butyl caritel and 40 wi % of solid content, example? A. Pepa of {0m aliptnpetiysno pops valebeaine ton67 c ~~ & \ AW No; {0068} A. inne of aly2-Q6N-tinesylaminoxsi ‘ether (11.88 g, 0.1 mol) and butyl glycol (40 mil) was heated to 60°C, and 1,3-propane sultone (11-56 g, 0.102 mol) was added dropwise to the mixture. The mixture was stired for 1 howe at 60" C., ad a farther 4 hours at 108° to 110°C, Water (2.0m) was added tothemixture while cooling to 90°C.,and the resulting mixture was stired at 95° C. for 2 hours 10 destroy the excess sultone, Water (35 mil) was added and the rmixtute shaken for minute and allowed to stan for 15 min. ‘Themixtare was extracted with ether and the water layer vas ‘exporated to dryness under vacuum. The ene procict Was pnfied by column chromatography, cling with methanol methyl acetate, providing the prodect 1 (16.8.2, Oct. 24, 2013 yellowish transparent viscous liguid which erystallined as peedlelike erystals on standing at room temperature for 3 days, B. Preparation of N-(propylsulonate)-NN-imn- ellyh2-([QE2}-445.566.7.78899.9aridecat- Ioro-2-nonen--yljoxyfetylamino}-1-propaniam, incr salt [0069 DOA Noo cca | Cm AN ~~ LANA, [0070] Petfioeo n-hexyl iad (0-C,F 1, 17.84 g, 0.08 sol) and HOCH,SO;Na (0.31 g, 0.003 mol) were shaken intl the purple color of ixtne disappeared, alter which 10.25, (0.0408 mol) of product 1 3.36 g, (0.04 mal) NaHCO,, (6.36 g, 0004 mol), water (40 ml) and ethanol (40 ml) were added. The misture thea was sired at 75-80" C. for hours. Soa hydroxide (1.6 p, 0.08 mol) in 10 ml of water was ‘added andthe clear reaction mixture ume dark brown, Aer hours stierng st 70-75°C. the reaction wasallowedio stand ‘overnight at room temperature, The erde product (24g) Was joblained after filtration and removal of solveat in vacuo. ‘Recrystallizatioa from ethan provided the purified product (4, 40%) asa brownish solid Example 3 Preparation of N-(Carboxymetbyl)-N.N-cimethyl-3- [QE2)-44.5.56.69,7 889.9 S-ridecalluono- nonen-I-ylJoxy]2(eiethy siloxy)peopslamino}-1= ropanium, inner salt [0071] [0072] Perfhioeo n-hexyl iodide (0-C,y 1, 14.72 8, 00 vol) and Rongalite (HOCH,SO,Na, 0.254 g, 0.00165 mol were shaken until the purple color of iodine disappeared, ater whieh 9.83 g (0.034 mol) of product 2, NalICO,, (2.77 0.033 mol, water ($0 ml) and ethanol (50 ml) were ado “The mixture then was tiered at 75-80" C. foe 4 hours. Soin fnydowide (1.32 g 0.033 mol) in 10 ml of water was added ‘and the clear reaction mixture turned dark how, After 2 fours string at 70-75° C. the reaction was allowed o stand ‘overnaht at room temperature. The erude product (23) wasUS 2013/0277597 Al Example 4 A: Preparation of 3-{2-propen-L-ylloxy-2-aydroxy) propylthio -propylsulfonate ether 0073) [0074] To a mixture of 3-mereaptopropanesulfonic acid, Sodium salt (108g, 0.52 mal) and 800 gf, was added 09 ‘go NaOH to adjust the solution pH to 89.58. g (051 mol) ‘oF ethyl glycidyl ether was added at room temp, over 0.5 he tnd the resulting mixturea then stiredat 65-75" cwemght after which sodium bicarbonate (3g, 0.5 mol) was added, This reaction mixture was carried on crude, [0075] _B: Preparation of 34{(2E/2}-4.4.5,5.66,7.7 889. 9.9-rdecalluoro-2-nonea-L-sl}oxy]2(ivdroxy propythio] propylsulfonate ether a aa Coal 10076) Rongaite (08g, 02005 mol) and 34.6 g (0.1 mol) of -C,F 1 were shaken until colorless and then added to the ‘enide reaction mixture, The mixture thea was slired at 75-80°C. for Shes. Anaddtional 20 yof n-CF Lwasadded unt the solution became clear NaOH ((4.0 2, 0.1 mol) was ‘added, followed by siting at 70” C. for 2, Solvent was removed in yet and the resulting proiet dried ina 60°C. ‘oven, The product was recrystallized from ethanol water (0 provide 45g ofa yellowish solid (88% ye), Pxample 5 3: Formulations and Test Results 10077] _A stock solution was prepared using butyl carbitol (18.9% w, laueyl dipropionate (4.0% wt), deeyl sulfate (1.6% w, tolytiazole (0.02% wt), and water (75.48% wo) ‘Table | describes the preparation of the AFFF concentrate using the spevitie compounds of Formula I. For comparison purposes, two analogs of compound (b) shown above also were prepared by the method exemplified in Example 1B. ‘These’ compounds are described as compounds (k) (REG,F, and () R—CyF,) espeetively in Table? below. Oct. 24, 2013 All concentrates made were based on rine content and the calculated weights of fluorosurfactants were adjusted for parity TABLE | ah Pasion af Fi Fins um Conscnnic Compound 90 Se Ss de tae 0078} ‘The ensving concentrates were diluted into 97 parts Synthetic sea water to form a premix, charged toa premix holding tank, and the tank was pressurized to 10 psi using compressed ai. 1 square fot test pan was filled with SOO mL of water and 500 mi of heptane, ignited and allowed t0 bum for 10 seconds. Foam was generated through an air aspirated nozzle and then applied to the heptane fire for 2 pawimum of 60 seconds. Extinguishiment times (Ext) were recorded and then a small burn back cup was placed in the ‘eater ofthe fire test pan. The fel in the cup was ignited and the time ittook the fire to cover 100% of the pan was recorded as bum back resistance (BB). The specific compounds of Formula I were compared based on extinguishment and burn back resistance. 0079} Foam quality was determined by placing 100 mot ‘remix into a blender ad mixed at the lowest setting for 1 ‘minute. The foam generated from the blender was poured into 4 1000 ml. greduated cylinder and the volume recorded. Foam expansion was calculated by dividing the recorded volume by the staring volume. The quarter drain time was recorded asthe time needed for 25 mi of figuid to collet at the bottom ofthe graduated eylinder.The following table ists the results, “TABL iss Resin an Qual Messrsneas Coupes _G)_initsee)_ in) _ nin [0080] Compounds (a) performed as well asthe com- mercially svailable product APC-SA. The commercially available product can contain C, homologues and flurosta-US 2013/0277597 Al bilizers thas bee found that semoving both; homologues and the Auorestbilize aiversely alles the products ire performance, Compounds (a)-) were tested as standalone Aorosurfatans ad the eile est resus indicated Ut ‘sompounds sch s those shown he table can be se asa Substitute forboth anionic andamphotece erin surf tants and as a foorostbiizer replacement, Full scale fire testing fit shown that composnd ()-) ean be ose at significantly redvced fone content aod sill meet third party approval entra, such as applicable Underwriters Tatoraory US and UK military specications. and eore- sponding sandards set fr bythe Europea Union 10081) Thetesting also showethat the compositions main- tained their perormance in brackish water sd see Water hich is diffieul o accomplish wit the existing commer: Sally salable materials. 10082] Fire perfomance results far the Military Fire Test F-24385 on regular gasoline larer demonstrated that com- pounds (3-6) can replace an anionic Nuorosurfactant a Fooratabilizee with an overall 25% redvetion in vrin. ‘Testing showed that formelstion lacking « conventional Aiyrestablzer could sill moet the test specications, Con- ‘cational hioeostabilzersaretypically wed to improve bu backresistance and increase the longevity of foam peodct. “heabiliy of eam compeniions es deserve herent meet the requirements ofthe Military Fire Test in theabsence of 2 ‘conventional Muorostabiice was very unexpected 0083} The Miltary Fre ‘Test also requires that the fre Fahing foam products be tested at «wide range of propor ning percentages to ensure that a weak or rich proprtioned luc ean sll meets he Hire test eure. Even pro- Portionedat half strength with redid setive component the Formation described above met the est rogueemeat 0088) _Panhertstingon this composition onthe UL Sprin- er Fo Tes witha reduced Norte loafing gave exeliont resus hase onthe dearee of difclty associated withthe ‘water deluge specification ofthe sprinkler ts, Even ata 25% Fecbiction in Boorine the composition mt hoth the extin- fuishment and bum back requirements of the UL Sprinkler Fire Test 1. An aqueous film-fireighting composition concentrate ‘comprising: (an effective amount of a monomeric C, perfhioroalky! ‘surfactant having a molecular Weight of less than 800 daltons, wherein said surfactant is zwinerionic or (&)an effective amount of a foam stabilizing agent, and () an effective amount of at least one non-uorinated surfactant, herein said composition bas less than 0.8% P, and is substantially free of any surfactant containing a perfhio- way] group containing more than 6 carbon atoms and ‘wherein said composition mests Military Specification MIL-F-243857. 2. The composition according to claim 1 wherein suid ron-Ahorinated surfactant is an anionic surfactant 3. The composition according to claim 1, wherein sad ‘oam stabilizing agent is a glycol ether. 4. The composition aeconding to claim 1, further compris ing comrsion inhibitor. 5. The composition according to claim 1 wherein said ‘monomeric Cperfluoroalkyl suretant is zwiterionic, Oct. 24, 2013 6. The composition aeconting to claim 1 wherein said monomeric perilorcalkyl surfactant has a structure repre- sented by the Form RX YLZ, ' wherein Ryis Cy straight or branched chain perihoroalky: X ig CC, straight or branched chain alkylene, or C.-C, straight orbranches chain alkenylenecontaine ing 1or 2 alkene moieties; ‘Yisselected from the group consisting of S—CH,CHIRCON(R?)—, —O—CHCH—NIR?) ie 0 CH,CHOR')CH, NOR YR4)—; —O—CHCH (oR')CIL,—-S—3 SCH COR CH NR YR and S—CH,CH(OR®)CH,—S Lis C.-C, sight orbranched chin alkylene, where one ‘urbon atom i the chain oplionlly 3 replaced by NOOR) and Zi O80, $0.0 COs ‘wherein R', RE, RE R® and Ry independently are H or Stright or branched hain Cy-C, allyl and Ris H oF Sng or branched chai CC, alk o aly 7. An aqueous flsizefihtng composition eoneentate comprising (@)anelfetive amount of a perfuoreally surat hay ing # structure represented by the fom wx 1 whersin Ris C, stright or branched ean peeluoroay, Xi C.-C, straight or bch chu allylene, or C-C,saightorbranchedebanalkenslene eontin- ing 1 or afkene motos YY is selected from the group consisting of S-CILCIRICON(R?)-,O--CH,CH, N(R) Re) —0--CH.CHOR'CH, NR KR); —0-CH,CH (ORCI S—; —S—CH,CHOR'} CH NVR: and S_ CHCHOR CH, —-S LisC,-C,, straight orbranched chain alkylene, where one carom atom in the chain optionally is replaced by ind Zs —O80;-,—$0,-, or CO, ‘wherein R!,R®,R®, RS R® and R’ independently are Hor straight or branched chain C,-C, alkyl, and RY is H or Straight or branched chain C,-C, ally or trialkyliy (®)an elective amount of a foam Stabilizing agent, and (6) an effective amount of at least one non-luorinated surftant, ‘wherein said composition does not contain an effective ‘amount of perflarinated surfactant that does not con- form to formula 8. The composition according to claim 7 witerein said on. fvoriated surfactant i an anion surat 9. The composition according to elsim 7, wherein ssid ‘foam stabilizing agent is a glycol ether. 10, The composition according to claim 7, further eompis- {ng a corrosion inhibitor, 11. The composition socording to claim 7, wherein Y is $= CH,CR'CONR?)— 12, The composition acconding to claim 11, wherein Ris Hor straight bain alkyl and Ris H.US 2013/0277597 Al —0-CH,CH, NRE — 14.Thecomposition according wo claim 13, wherein Rand Rt are Hor methyl 15, The composition aecondng to claim 7, wherein Y is O-CHCHOR CH, NBR) 16.Thecomposition aeconding to claim 18, wherein Rand Rare Hor methyl, and Ris Hor tiakysily 17. The composition according to claim 7, wherein Y is —0CH,CHOR'}CH, 18. The composition aeeonding to claim 17, wherein R* is Hor alkyl 19. The composition aecording to elaim 7, wherein Y is S—CH.CHOR')CH, NOR XR?) 20. The composition according claim 19, wherein R*and “are Hor methyl, and Ris Hor wialkysily 21. The composition acconting 10 claim 7, wherein Y is S$ CHCHOR ICH 22. The composition seeonding o claim 21, wherein R? is Hor talks 23. The composition according to claim 1 or claim 7, further comprising an alkylpolyglyeoside in the amount of 0310 7%. 24, The composition according to claim 1 or claim 7 further comprising a polysaccharide gum in an amount of 0.1 05%, 28. The composition according to claim 7, comprising s platy of perfuoroakyl surfactants othe formula 26, The composition according to claim 1 or claim 7, wherein sid foam stabilizing agen is present in an aanoutt of 1-50%, said non-fuorinated surfactant is present in an amount of 0.1 to 30% and said peefiaoroalky] surfactant oF mixture of surfactants of formula is present in an amount of 0510 20% 27. fire-fighting foam, comprising a composition accor ing to claim Yor claim 7, and an aqueous figui. 28, The foam according to claim 27, wherein said aqueous Tiguid is brackish water oF seawater Oct. 24, 2013 29, A method of making a fire-fighting foam, comprising foaming composition according to claim For laim 7 with ‘an aqueous liquid. ‘30, The method according to claims 29, wherein sid aque: ‘ous liquid is brackish water or seawater. ‘31, An aqueous film-firefihting composition concentrate ‘comprising () an ellective amount ofa perfluoroalkyl surfactant hsv ing a stricture represented by the forma we X¥La, 1 wherein Ryis C, straight or branched hain peruoroalkyl; X ig CC), straight or branched chain alkylene, or C.-C, staightorbranchedehanalkensleneeontine ing 1 or afkene motos YY is selected from the group consisting of -SCULCHRCON TRE), OCI CH, NR) R —0—CH,CHIOR')CH, NVR}; —O-CH,CHL (ORC, Ss —S—CH,GHOR CH, NR VR and $_ CH,CHOR CH, —S Lis CC; tight orbranced chain alkylene, whereone cafbon atom inthe chain optionally replaced by NIRoKR Z's 080," $05, 01 CO; ‘wherein RR? RY Ran adependenlly are H or Siaight or branched chin C,-C, allyl and Ris H oF Suit or branched chin Cy -Cy alk ala i (©) an effective amount of a Moornated foam stabilizing ‘gal containing 3107 periuorinated carbon soms, ad (6) an effective amount of at least one non-oinated ‘sifatant, and ‘wherein said composition doesnot contain an effective ‘mount of prfvrinatelsufatast that Joes nt cone foto formula L