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