'US 20080251 751A cu») United States cz) Patent Application Publication co) Pub. No.: US 2008/0251751 Al oy os) om en @ Bruckner et al. SILICONE SURFACTANT COMPOSITIONS AND USE THEREOR FOR GENERATING FOAM Inventors: Arndt Bruckner, Muiheim ad Ruhr (DF); Dirk Kuppert, Recklinghausen (DE) Comesponilence Address: FROMMER LAWRENCE & HAUG 74S FIFTH AVENUE- 10TH F NEW YORK, NY 10181 (US) Assignee: Goldschmidt, Essen (DE) Appl.No: 121099, Filed: Ape: 9, 2008 (43) Pub, Date Oct. 16, 2008 G0) Foreign Application Priority Data Apr. 10,2007 (DE) 10 2007 0169665 Publication Classification Gl) Ine. 62D 04 (2006.01) (2) US.EL 25213 on ABSTRACT Te present inveation relates to compositions having organo silicon compounds for generating, foams, where the organo- silicon compounds have sulphonate groups and Si—O—C Tinkages, and also wo the use of these compositions for pro= ducing aqueous foams, in particular fire-extingushing foams ‘nd cleaning foams,US 2008/0251751 AI SILICONE SURFACTANT COMPOSITIONS. AND USE THEREOF FOR GENERATING FOAM [0001] This application claims benefit under 35 U.S.C. 119 {)of German patent application DE 192007 016 966.5 0n 10 Apr 2007, [0002] Any foregoing applications, including German patent application DE 10 2007 016 966.5, and all docaments ‘ited therein or during their prosecution (“application cited ‘documents") and all documents ited or referenced in the ‘application cited documents, und all documents cited or rel ‘erenced herein (herein cited documents"), and all docu ‘mens cited or referenced i herein cited documents, together ‘with any manufacturer's instrictions, deseriptions, product specifications, and product sheets forany preducts mentioned herein or in any document incorporated by reference herein, are hereby incorporated herein by reference, and may be ‘employed in he practice of the invention. 0003] The invention relates to the use of organosiicon ‘compounds containing sulphonate groups for generating !qucens foam which caa he sed on ydopbobie igus, and ‘© foam-loming substance compositions according to the 10004] Aqueous foams are suitable for diverse application purposes for example in the field of cosmetics for producing shaving foam or skincare composition, inthe domestic or Jndustrial sector for cleaning purposes for suppressing dst ormation, for papermaking, for dyeing processes, for the Jactionation or separation of metal orsalts thereof, for insu- Tating ice surfices, for the manufacture of eoncrete and ‘cement, for protecting. surfaces, buildings or vegetation ‘agunst fie andor heat, for fighting fire, ineluting fires in ‘ines, and for fost protection of plants. Por amore detailed ‘explanation of some ofthese applications, reference may be mde tA. R. Aidan, C.S. Grove I, D.N. Meldrum, Novel Uses of Aqueous Foams, Chem. Eng. 1964, 71, 145-148. Moreover, there sa need for foams lor applications in whic the foam comes into contact with nonagueous liquids, seh as, for example, ominic solvents or petrochemical fuels, ‘energy fuels (and engine fuels) and in whieh the foam has to have adequate stability and flowability. These applications Include, inter ali, the cleaning of installations such a8 oil depots, pipes pipelines or drums, the reduction inevaporative Josses of volatile ydrocarbons or other organic solvents or firefighting. Thus, it known to fight fies, in particular of Juels, by applying continuous layers of foam. Such layers of am are also stable for preventing fires from breaking ut. For generating these foams, use is usually’ made of foam ‘compositions which form Water-contaning film benwecn, foam and combustible liquid Aqueous. Film. Forming Foam’”—AFFF or A3P).This film ensures rapid spreading of the foam and providesa vapour-tight barrier and thus prevents reignition, AS an essential constituent, AFFF comprise st= ‘actants having perfoorinated groups. Foam compositions oF this type are deseribed, for example, inthe specifications DB-12 16 116 (US. Pat. No. 3,258,423 A), EP-A-0 $98 772 (US. Pat. No, §.496,475 A), US. Pat. No. 4.420.434, DE-23 57 281 10005] | DE-22 40263 claims foam-forming substance com- Positions which consist of 0006] a) foaming agent, which, for example, may be a Tong-chain polysioxane with attached sulphate groups, Oct. 16, 2008 0007] b)anS—or Ofoweralkyl)-substituted oxy acid ‘of sulphur ora salt thereof, and unconditionally [0008] ) a surfce-sctive agent of tetafhioromethane, [0009] DE-18 12 531 (US. Pat. No. 3,655,555) discloses that watersoluble polysiloxanes can be used as slubilizers {oronganic Nuorine compounds for generiting aqueous fie extinguishing foam concentrates. [0010] US. Pat. No. 3.849.315, US. Pat. No. 4,038,195, US. Pat. No. 3,957,657 and US. Pat. No. 3,057,658 disclose extinguishing foam mixtures comprising silicone surfactants ‘which roquire the presence of surfactants wit peruorinatd soups. The mixtures of surfictants with peruorinated soups and silicone surfactant are themselves not adequately Taming and therefore bave tobe improved in terms oftheir foaming. ability by adding surfactants which coatain neither perfluorinated groups nor silicon atoms. In contrast to the ‘compounds according to the invention, the described silicone surfactants are purely Si—C-linked, fe. the radical carving the ionic charges bonded othe organosilicon radical only by ‘an Si-C bond and not to certain Iractions also via an Si-O bond. [0011] ‘The specification family DE-28 26 224 (US. Pat ‘No. 3,849,315.A), WO-A-80/01883, U.S, Pat, No, 4464267, US. Pat. No. 4,387,082, US. Pat No. 4,060,489, U.S. Pat No, 4,149,899 and US. Pal, No, 4,060,132 teaches fire-ex- tinguishing foams for buming hydrophilic liguids which comprise a polysaccharide and optionally silicones andor ted lydrocarbons. The Bgrinated hydrocarbons c ally also be omitted, although only their presen ‘makes the formulation, following dilution and foaming, into effective fre extinguishers on hydrophobic liquids such as petrol, The surface-active silicones or the Fluorinated! hydro farbons serve there to generate an aqueous film, but them selves do not foam io an adequate degree. Yet furter, surface- active substances which are neither oorinated hydrocarbons ‘or slicones are ruined to impart the desired foamabilty to the compositions. In contast othe compounds acearding 10 the invention, the described silicone surfactants are purely SiC-tinked, ie. the radical carrying the ionic charge is only ‘bonded to the organosiicon compound by an SiC hondand ‘otto censin factions also via an Si-O--C bona [0012] In the context of inereasing environmental aware- ess, however, fuorine-containing compounds have inereas- ingly been the subject of ertcism in recent years on account ‘oftheir extremely low biodegradability and in some instances high residence ime in the organism (M. Fricke, U. Lah, Risk assessment of perfhioro surfactants as contribution to the eeurtent discussion othe REACH dossier athe EU Commis sion, UWSP-Z, Umwelichem. Okotox. 2008, 17, 36-49). la 2005, Sweden proposed in the course ofthe Stockholm Con- vention on Persistent Onzinie Pollutants, a world-wide ban orperfiuorooctanesulphonates(PFOS) customary ing cents and starting materials for AFFP. The person skilled inthe artean expect thatthe use of surfactants containing pefivor- ‘ated groups will become restricted in the future for reso ‘of envitoumental and health protection, and, even if heir use were to be exceptionally permitted for extinguishing applic ‘ions they will only be available at increased prices duc tothe reduced production volume. There is therelore a need for oam compositions which are suitable for fighting solventand Tel fires and which make do without ora least with a sig- nificantly reduced fraction of surfactants containing perth orinated wroupsUS 2008/0251751 AI 10013] The application specification WO-A-2004112907 (US. Pat. No. 7,005,082 B2) discloses a foam composition ‘concentrate based on high molecular weight polymers with ic functionalities in combination with metal salts which ‘does not require organic Duorine compounds. The metal sls described therein include the toxie salts of, for example, antimony, barium, copper, thallium or tn 10014} Ic is prior art that onzanosilicon eo sulphate andr sulphonate groups can form aqueous Fons. DE-17 45 514 (US. Pat. No. 3.513.183) describes silicone sulphatesand their use as wetting agents andemlsiiers. US. Pat. No. 4,960;845 describes the use of organs pounds whieh cary sulphated polyether radicals. Sulpho- nated polyethers ate not mentioned. The use s surfactants for ‘extinguishing fires is likewise not mentioned, USS. Pat No, 6,777,521 discloses compounds which carry. sulphated troupe of the type Si(CH,}y OCH, -CH(OH) CH, — ‘SO, and their use in polyurethane foams and cosmetic for- ulations. The use as surfactant fr generating extinguishing am for fighting fires is not disclosed, The disclosed com Pounds exhibit unsatistsctory foaming ability on hydropho- bie surfees. [0015] The laid-open specification DP-1668 750 (US. Pa. No. 3507897) describes surface-aetive compositions based ‘on rganosiicon compounds which contain sulphonate jaroups and their use as foam compositions, emulsifiers and ‘wetting agents. The organosilicon compounds re character- ized in that they contain groups ofthe type—Si(CH,), —O- CH, —CH(OH)—CH, $04, [0016] The laid-open specification DP-1 768 252 (US. Pa. No.3.531,417 teaches the preparation of polyether iloxanes ‘containing sulphonate groups and mentions their suitability as foam compositions. The use as surfactant for generating ‘extinguishing foam for fighting fires is not disclose. The disclosed compounds exhibit unsatisfactory foaming ability ‘on hydrophobic liquids. [0017] was an object of the present invention w provide altemative compositions for generating foams which do not have one or more disadvantages of the concentrates of the prior art. The foams produced from the compositions should particularly preferably huve a high stability on hydrophobic Fiquids without of with only a small addition of foorine- ‘containing compounds. Furthermore, the altetive compo- sitions should be easy and cost-effective to produce 10018] Surprisingly, it hus been found that this abject is chieved by compositions which have organsilicon com- pounds containing sulphonate groups and having Si-—-O—C Finkages. Neither improved fosming behaviour of completely ‘or partially Si—O—C-linked sulphonate-grovp-containing ‘organosiicon componnds, nor the useof these compounds as foam compositions for fighting fire, in partiular for fighting {vel fires, without the obligatorly roquired addition of sur- ‘actants containing pervorinated groups ean be dxvced oF derived from the prior an. The suitability as extinguishing ‘oamis completely unexpected forthe person skilled intheart in panicular inasmuch as the fat that organosilicon com pounds containing sulphonate groups used aecording to the Prior ant for extinguishing foam applications always require the presence of srfictants containing perfuorinated groups {or generating foams of high stability that can be applied to or ‘on hydrophobic liquids Oct. 16, 2008 [0019] ‘The object of the present invention is therefore ‘composition having onganosilicon compounds for generating ams (oam compositions, which is characterizedin that the ‘composition comprises one or more onganosilicon com- pounds which comprises [0020] a) at least one siloxane unit of the formula (1) RERO}SIO crate ©, [021] where [0022] _R" and R? are one or more identical or different radieals independent of one another and selected from linear or bratched,saterated, mono-or polyunsaturated alky haloalky| ary, alkylaryorarylalky] radicals hav ing | to 30 carbon atoms, where the radicals may option- lb ier yon ur ony a i jms andior may optionally have a —OC(O}CH, fou onthe nd ofthe cic, 0023] w is, 1,2 or 3 and [024] xis 0.1.2 oF3, where the sim wx is not >3, [0025] _b) optionally one or more siloxane units ofthe gen- cna Formula (VD) RAR cesys wn, [0026] where 0027] RY isas R' defined in), [0028] y is 0, Lor 2 and 0029] Ris group ofthe formula A By-C-DyLLy [0030] where [ost] eis [0032] b, ,dand eare or 1 [033] Tis 1 and [034] asbsezt, where [0035] _ isanoxygen stom, a CH, groupora CH=CH ‘wou, [0036] Bisa group ofthe geneva formula (Il) 4p [0037] where [0038] mis an integer from 0 0 30nd [0039] |G may bea divalent group selected from linear or branched, saturated, mono- or polyunsaturated alkyl, aryl alkylary] or arylalkyl groups having 110 20.arbon atoms, [0040] © is a CH, group or a divalent radical selected from linear or branchod, saturated, mono- or polyun- saturated alkyl, aryl, alkylaryl- or arylalkyl-oxy groups having 1 to 20 carbon atoms or @ group of the formula —CH1,—O-(CH,),-O— 0041] Dis 2 group of the general formula (1V) ACMANCHO {Coll CO. — w, [0082] where [0043] n, p,q and rare integers from 0 10 50 indepen- dently of oneanother, andifmore than oneof the indices is n, p,q. 0, the general formula (IV) is a random ‘oligomer or a block oligomer,US 2008/0251751 AI loos Hack [Eis agroup ofthe general formula (V) [o0gs] where [oog6] wis an imeger from O10 Sand [0047] ifuis>0, may be ideatical or different andis3, 4or5,and [0048] Lisselected from theyroup comprising hydroges atoms, linear or branched, saturated, mono oF polytn= saturated alkyl ary, alkylary or arylalkyl groups hav- ing 1 10 12 carbon atoms, acetoxy, groups, POH, soups, PO,H 1M groups and PO,?" 2/.M"™ groups ‘where M™ is av-valent cation where 049} vis 1,2, Sor, and 0050] )at least one siloxane unt ofthe fore (1) whic ‘has at least one sulphonate proup, BERS coins w. [W051] where [052] R°iso6 R defined under a) [0053] 2350, 1 or 2 and [054] Risa group of the Formals [058] A,-B,-C--Dy-E-F,-SO. 1M", [056] wits [0057] a, ¢ and fare 1 [0088] bande are O or 1 and [059] din at least 70° ofthe radials R®-1, where [0060] B.C, D, F and M™* can have the meaning as aivenin), [0061] F is’ divalent radical selected from linear or ‘branched, saturated, mono- or polyunsaturated alkyl, aryl alkylarylorarylalkyl groups having I to 20carbon atoms and 0062] Misa v-valent cation where v=1,2,3 oF4, with theproviso thatthe radial A in Sto 100% ofthe radicals Aig an oxygen atom and in Oto 98% ofthe radicals Ais CH, group andlora CH=CH group. 10063] The present invention likewise provides the wse of 2 ‘composition according to the invention o ofthe organo ‘con compounds present in the composition according to the invention for prodoing foam, i pail an neous 10068] The compositions according to the invention have the advantage thatthe foams obtained from them are also sulicently stable on hydrophobic and possibly combustible ‘materials, in particular igus, and can thus also be applied to such materials, As a result the foams produced from the ‘compositions acconding to the invention, in particular aque- ‘ous foams, are exceptionally suitable as fir-extingushing ‘oams, covering foamsor cleaning foams, in particular foruse Inthe presence of hydrophobic materials, in particularhydro- phobic liquids. [0065] The composition aceording to the invention bas, particularly asa result of te stability ofthe foam produced therefrom without the addition of surfactants containing per ‘Tuorinated roups, the advantage thst, upon using te foams, no organoflvarine compounds pass int the environment. [0066] The compositions according to the invention and & process for their preparation and also their use are described Oct. 16, 2008 below by way of example although the invention should not beresricted to these exemplary embodiments, Where ranges, general formulae or compound clases are stated belo, thea these should include not only the corresponding ranges or saroups of compounds which are explicitly mentioned, but also all part ranges and subgroups of eompounds which caa be obiained by aking out individual values (ranges) oF com pounds. Where dociments are cited in the course of the resent description, then their entire content should form part fof the disclosire conten of the present invention, [0067] Iris noted tat in this disclosure and particulary in the claims andlor paragraphs, terms such as “comprise”, comprised”, “commprising” andthe like ean have the meaning attibuted tit in US. patent law: e2, they ean mean “ineludes”, “ineluded”, “ineluding”, and the Hike; and that terms such as “consisting essentially of and “consists exsen- ‘ally of” have the meaning ascribed to them in US. patent Ja, eg they allow for elements aot explicitly recite, but exclude elements that ace found inthe prior art or that affect ‘abasic or novel characteristic of the invention, [0068] » Tes futher noted thatthe invention doesnot intend oencompas within the scope the invention any previously disclosed product, process af making the product or method ‘fusing the product, which meets the written description and ‘enablement requirements ofthe USPTO (35 U.S. 112, fst paragraph) or the EPO (Article 83 of the EC), sued that applicants) reservethe right and hereby disclose a disclaimer ‘of any previously described product, method of making the product or process of using the produc. [0069] Compositions for generating foams are understood below as meaning compositions which are suitable for form- ing foam by introducing gas bubbles, in particular by ‘mechanically introducing gas bubbles and very particularly preferably by mixing in gas bubbles, in parieular air bubbles, Jno extinguishing water which comprises the composition ‘according tothe inveation, [0070] The inventive composition having organosilicon compounds for generating foams (foam compositions) is characterized in tal the composition comprises one or more ‘organoslicon compounds which comprises [0071] a) atleast one siloxane unit of the formula () RERODSIO ovate ©, 0072] where [0073] _R" and R? are one or more identical or different ‘dicals independent of one another and selected from Fincaror bratehed,savrated, mono-or polyunsaturated alkyl haloalky] ary. alkylary orarylalky] radicals hav ing 14030 carbon atoms, where the radials may option- ally be interrupted by one or more oxyzen andor nitro- ‘gen atoms and/or may optionally have a —OC(O)CH, ‘group on the end of the rede 0074)" is 01,2073 and [078] xis 0.1/2 03, where the sum 4x isnot >3, [0076] b) optionally one or more siloxane units ofthe gen- cra form (V1) 0077] where [0078] | R°isas defined ina), [0079] y is 0,1 or2 and [0080] Risa group ofthe formula A,-By-C-De FL, fous] where [02] ais 1US 2008/0251751 AI Woosa} bc. dandeare or, fos} Lis [boss] sb whee [0086] an oxygen atom, a CH, group ora CH=CH group, [0087] is group of the general formal (I) am tub fooss] where [089] mis an integer from 0 t0 30 and 10090] _G may be a divalent group selected from linearor Drauched, ssturated, mono- or polyunsaturated alkyl, aryl alkylary| or arylalkyl groups having | to 20.carbon atoms, [0091] Cis 8 CH, group or a divalent radical selected fiom linear or branched, saturated, mono~ or polyan= saturated alkyl, aryl, alkylary! or arylalkyloxy soups having I to 20 carbon atoms ora group ofthe formula —CH,—O—(CH,),-O- [0092] Dis group of the geteral formula (IV) ACHOWCHOYC oH OL.CO.— w fo093] where [094] a, p.q and rare integers from 0 to 50 indepen- dently of one another andi more than one of te indices is, p,q, 0, the general formula (IV) is a random oligomer ora block oligomer, [098] isa group ofthe general formula (V) find “ [0096] where [097] us an integer from Oo $ and [0098], ifuis>0, may be identical or different ands 3, 4075, and 099] "Lisseletod from theyroup comprising hydrogen atoms, linear or branched, saturated, mono- oF polyun- sturated alkyl, ary, alkylary or arylalkyl groups hav- jing 1 0-12 carbon atoms, acetoxy groups, POSH, ups, POH 1/v M™ groupsand PO?" 2/v M™ groups ‘where Misa v-valeat cation where [o100) vis 1,2,30r4, and [0101] cat leastone siloxane unit ofthe Formula (11) which hha at least one sulphonate group, RERSOjrcssne w, [102] where [0103] R°isas R defined under a) [104] 2180, 1 or Zand [0105] R* isa group ofthe Formula Ac Be CoDe Bef SOF [0106] where [107] a, cand fare 1 [108] bande areOor 1 and Oct. 16, 2008 [0109] din at least 70% ofthe radicals R°1, where [otto] 8,8, C.D, E and M'* can have the meaning as sven in’), [0111] F is a divaleat radical selected from linear oF ‘ranches, saturated, mono- or polyunsaturated alk, aryl alkylary or arylalkyl groups having 110 20 carbon atoms and [0112] " M'*isav-vatenteation where v1, 2,3 or, with the proviso that the radical Ain St 100% ofthe radials A isanoxygen atom and in to 95% ofthe radicals Ais 4 CH, group andlor 8 CH=CH group. Preferably, the radial in the sum ofthe siloxane units ofthe formula {and optionally (VD), in particular in formu (I, is an oxygen atom 0 7.5 to 75%, preferably 0 1010 50% [0113] In anotier embevdiment ofthe invention, in the at Jeastone siloxane uit ofthe formula (), atleast one of w and isnot ze, [0114] It may be advantageous if the orzanositicon com- pounds having siloxane units of the formulae Dy, (1) and ‘Optionally (VD) of the compositions according 1 the inven- tom have, on average, arti ofthe numberof sileon atoms to the numberof sulphonate groups of from 1.51 to 20:1, preferably from 20:1 10 10:1, with preference from 22:1 t9 41 [0118] Preferred compenitions according tothe invention ‘hve organoslicon compounds which have siloxane units of po the formula (1) where R=CH, and x-O, siloxane units ofthe formula (1) where R'~CH, A-oxygen atom oF CHT, proup m0, C-CHf, soup or CH,CHO group, n and integers from 0 10 30 independent of one another, q-r-U-0 F-CHLCH, group or CH,CHCTTs group and siloxane units ofthe formula (V1) where RCH, and y-1 0 2. [0116] Paricularly prefered compositions according 1 te invention have orgzanesilicon compounds which have siloxane units of the formats (}) where '~CH, and x-0 and siloxane units of the formula (1) where R®-CHy, A-oxygen atom or CH, group, m-0, C-CH, group oF CH,CH.O group, n=integer om 0 10 20, p=4=r-U-0 and P-CH.CH, group of CH.CH,CH, group. [117] _ Very purcularly prefered compositions sceonding ‘othe invention have orzanosilicon compounds whieh have, onaverage, 0t0 30 mol %of unitsof the formula (2) where RCH, group, w=l,x-0, (0095 m01% ofunitsof he formula (D) whereR'=CH, group, W200, (010 70mol%of unitsof the fem (where W380, 10 w 98 mol % of units of the formula (II) where R*-CH, group, 7-1, ABC> CH, CH, -CH,-O-, ne20, poqreu-0,F——CH,—CH,CH, O20 mal fy fh oma I) we RY -A-Oand BC: Rec Soe tients, (0 to 20 mol % of units ofthe formula (I) where R group, 2-2, A-Oand Be CH CH. —SO, Uw M™, (010 20 mol 9% of units of the formula (II) where R°=CH, soup, 2-3, A-O and B-C-D-E-F-SO,” Iw M'~CHy CHyCH, SO," Liw Mt", (040 30 mol % of units ofthe formula (VD) where R™=CHs group, yl, ABAC-—CH,—CH,—CH,—0— Brg r-t4), nspes0, C——CH;CHO— or —CHCH) Cij0 and Ls ental or diferent ad selected from the Hgroup, Hy E-F—SO3- liwM"——CHyUS 2008/0251751 AI roup consisting of —Ctly) (CH,),CHly, —(CH)sCH, BCHigsCls (CH,),CH. —CHCHSCH, an CH=CH cH,, (0% 30 mol % of Units ofthe formula (V1) whore R°-CH, grup, yl AO ru), aapeso. CCH,cH1,0— or —CI{CH,)CH,0— and Lisidentical ‘ordilfereat and sslctd fom the group consisting ol CH. ECU) -CTIy (CH) Cy. (CH1).CHy, (CHT Cu. CH CH, and —Chi—CH CH, {0118} 0 t0 30 mol % of units ofthe formula (V1) where RCH group, y-2 AO, meget uO, n4pes0, HCHO ar CHY(C1jCH,O~ an isidntial ‘or dfereat and selected from the group comsistingol CH, (CH.CHy, (CH, Ctl, (CH),CHy (CHB — Cul, CHI, and —Chi—CCH, and 0 1 30 mol % of units ofthe formula (VD) where R°-CH, grup, yO mgr tO, nepes0, CCur,c11.0— or —C1{CH)CH,0— and Lisidenical ‘ordilfereat and sslctd fom the group consisting ol CH. ECU) sCTIy (CCH. (CH1).CHy, (CHT CH, CH" CH, snd—Cii—CHCH, {0119} Inthesitoxane units, Mifpeterably selected from the catious ofthe roup K, No", NH”. GC\H, INH," 0 (CH).N"or(CH).N-R’RE, where R” andar dente or sifferet ally! madicals, in parla thse having 1 to 20 feo atoms, ora mixture thereat Ms particulary pre ferably Kor Nat [0120] Thecompesitions having orzansilicon compounds according to the invention for generating foams can have Turder customary adlves. In pact these may be 10121] 2) amphoverc hydrocaron surfatans, sch a, foe example, betanes and suiphobetaines, which are commer ally avilable, for example, under the tade names Texo tain 50 from Goldschmidt, Chembetain CAS (cocoa ridopropyTbeuine) fom Chemron, - Mizauine CS {@hodia} Mockam 2CYSF (Melnste), Deiphat D-160C (leaked 10122} ) anionic hydrocarbon surfctnts, such as, for example alkyl carboxylate, sulphates, sulphonates and cshoxylated derivatives thereof, a particular ot and av 1p dipropionates, sodium oetyl sulphate, sodium decyl Spats, sodiue dodeey! sulphate ammonium lay shor sulphats, 10123} ©) nonione hydrocarbon surictants, such a, foe cxampe, alkoxylate alkypenols, linear or branched Ssleohols and alkoxides thereof, sich, for example, ley Alcohol ethoxyltes, fatty acids an derivatives thereof atkylamines,alkylamies,actslene gyeols, gemini sur- Toctants, sch as, for example Suto] 104 (AiProduet) aliglalyeosides or polyglycosides, as described in U.S Pat. No. $207,932, or ethylene oxide-propylene oxide Hock polyeters, 0124) @) polymeric foam stabilizers andor thickeners, such, for example, procs or dewadation predicts thereat, such as, for example, arial hydrolysed pro- tens, starch, polyvinyl esas, seh a, fr example, pay Vinyl alcohol poyserylamids, earboxyviny polymers or polypyrolidins {0125} c) the combination, disclosed in WO-A.2008) 112907 (US. Pat. No. 7,005,082 12), with high molecular ‘weight acidic polymers and coordinating sls, 10126) 1 foam auxiliaries, seb as, for example, by dig Iycol, alyceml ethylene givea! monoalksl ster. icy. xe alco! monoalkyl ether, ethylene give monoalkyl Oct. 16, 2008 ether, propylene glycol monoalky] ether, dipropylene gly col monealky ether, tipropylene glycol monoalky] ether, | -butoxyethoxy-2-propanol or hexylene glycol, [0127] g)antitfeores, such as, for example, alkali metal or alkaline earth metal chlorides, ure, glycols or glycers, [0128] additives said to combat flocculation, separation ‘oreorosion, sch as, for example, etre aed, tartaric acid, polyaminopolyearboxylic acid, ethylenediamine tetra ates, o-phenylphenol, phosphate esters or tolyleiazole, [0129] 1) flm-forming additives, suchas, for example, the polysaccharides described in the specification family DE-28 26 224 (U.S. Pat, No, 3,849,315 A), WO-A-80) 01883 (U.S. Pat, No. 3,849,315 A), U.S. Pat. No. 4,464, 267, US. Pat. No. 4,387,082, US, Pat, No. 4.060.489, US at. No. 4,149,599 and US. Pat. No. 4,060,132, or xan- thn, pectin, slgin, spar, earrageen, pectic acid, starch, ‘modified starch, alginic acid, gum arabic, dextrans, celhi- lose, hydroxyalkyleelluloses, cellulose ethers and esters or the like, 10130} j) preservatives, as are commercially available, for ‘example, under the names Kathon CG/ICP (Rohn & Faas) or Givgard G-4-40 Givaudan), [131] k)woter, such as, for example, fresh water, drinking water, surface water, salt Water, sea Water or brackish 10132} 1) adaitives which are obvious tothe person skilled inthe art and are not fur desi here [0133] Tae compositions according othe invention can be used for producing a foam, preferably an aqueous foam. The ‘compositions according tothe invention can be uscd in pa ticular for prodicing fire-extinguishing. foams, exercise ams or foams for the cleaning of installations or appara- ruses, such as, for example, eil depos, pipes, pipelines oF drums, for reducing evaporative losses of volatile hydrvear- ‘bons or other organic solvents, and for preventing the break- ‘ut oF fires [0134] Ia composition aeconding to the invention is used {or producing fire-extingushing foams, it may be advanta- cous if surfsctants containing perlluorinated groups, Lor ‘example those as described inthe US. Pat, Nos. 4,060,489, 4420434, 4,472,286, 4,999,119, 5.085,786, 5,218,021 of 15,616,273, arethave been also added to the composition, [0135] Theamountsosurfactanteontaining perfiuorinated sroups are preferably chosen such that without the organo- silicon compounds aeeording to the invention, no extinguish- ing foam corresponding to the prior art could be obiined at the sited concentration of surfctant containing pecflvor- rated groups. In this way: an extinguishing foam can be ‘obiained which, upon use, has further impeoved extinguish- ing rateand a reduced risk of reignition. [thas been found that the total content of surfactants containing perfnorinated _aroups may be equal to or less than half of the conceatration ff surfactants containing peroorinated groups required for ‘zenemiting a comparable extinguishing foam (extinguishing oam with comparable extinguishing and stability properties) without detectable amounts of omganosilioon compounds ‘which have units according to formilae()and (I) as defined hove, [0136] Staring from the teaching of US. Pat, No. $207, 932, composition according to the invention therefore pref. crably ha les than 0.20% by weight of organically bonded ‘uorine, based on the composition. [0137] ‘Tae compositions according othe invention can be luted fo customary concentrations. Typical foam concen-US 2008/0251751 AI teateshave,forexample, fo 10 pars by mas, preferably 200 part by mass and particularly preferably 3 or 6 parts by ‘mass ofthe composition aecording tothe invention nd 99 10 90, preferably 98 10 95 and particularly preferably 97 10 96 parts by mass of extinguishing water, which may be, for ‘example, Fresh water, drinking Water, surface Water, sal, ‘water, sea water of brackish water. A 3% strength by weight qoam concentrate ths gives rise, a @ concentration 0.2% by weight of surfactants containing pertivorinated groups, 10 8 concentration of surfactants containing perluorinted ‘r0ups in the extinguishing foam of about 0.006% by weight. ‘The teaching nocording to the prior at as can be found, for ‘example, inthe above-mentioned specifications U.S. Pat, No. 3,840,315, US. Pat. No. 4.038.195, US. Pat. No. 3,957,657 ‘and US, Pat. No, 3:987,658, andalso he specifications of the ‘specification family DE-A-28 26 224 (US, Pat, No. 3849, 315.4), WO-A-8O/O1885 (U.S. Pat, No. 3.849.315 A), US. Pat, No, 4468,267, U.S, Pat, No, 4.387.032, US Pat, No. 4,060,489, U'S: Pa No. 4,149,599 and US. Pat. No. 4.060, 132, equites a five-fold to ten-fold concentration of surf: tants containing perfuorinated groups. 10138] ‘The compositions aceording w the invention canbe prepared in highly diverse ways and in various concent tions. In particular, thoy can bo prepared by mixing. Prefer tence is given to compositions according to the invention ‘which are prepared by mixing the organosiicon compounds whieh have units of the formulae (2) and (II) as defined above ‘with amphoteric hydrocarbon surfactants. anionic hydrocare bonsurfactants, nonionic hydrocarbon surlactants, polymeric foam stabilizers andior thickeners, high molecular weight ic polymers andlor eoontinating salts, foam auxiliaries, antifreeze, additives t0 combat floceulation, corrosion oF separation, film-forming additives, preservatives, water and !aditives which are obvious tothe person skilled in the at ia the concentrations which the specifications Tisted in this pplication teach, 10139] The oruanosilicon compounds present inthe com- positions according to the vention ean he prepared in varie ‘ous ways. For example, the organesilcon compounds which have @ siloxane unit ofthe formula (I can be obtained by ‘addition of hydrogen siloxanes onto alkenyl polyether sul- phonates(hydrsilylation) or by dehydrogenative eondensa- ‘ion of units carrying silane hydrogen with present polyether sulphonates containing hydroxy groups. [0140] The hydrosilylation of the sulphonates of alkenyl polyethers is preferably carried out in the presence of a pre- ‘cious metal catalyst in particular a rhodium of platinam ‘catalyst. Preference is giveno sing the catalyst nan amount ‘of from 5 ¢0 20:mass ppm of platinum or rhodium catalyst (ass fraction of precious metal based on the mast of the otal mixture). The catalyst is particulary preferably used in the om of hexachloroplatinie acid, cisplatinum, d-j-chlord- bis{chloro(eyelohexone)platinum(IN| oF Karstedt catalyst (optionally dissolved in solvents), or in the form of finely «divided elemental platinum on 2 carrier material such as ‘lumina oxide, sien gel or ative carbon, The hydrosily Jatin is preferably carried outa a temperature of fom 60 19 200" C,, preferably from 70 10 130° C, Preferably, the inytosilytion is carried out ata pressure of fom 0.9 10 20 bar preferably at 0.980 o 2 ba. Iimay be advantageous the hyeroslyltion i carried out in a solvent. Preference is given to using inert solvents, such as, for example, xylene or old- ‘ene. Solvents that can be used, however, are also alcohols, sueh a, for example, 2-butoxyetbanol, butyl glyco, butyl Oct. 16, 2008 glycol, isopropanol, ethylene glycol oF 1,2-propaneial, ethers, suchas, for example, di(propylene glycol) butyl ether ordi(propylene glyco!) methy ether, polyetiers, such a, for ‘example ally-, methy-or burl-stared polyethers or water [0141] Orzanosiicon compounds in whieh A in the units of the formula (VD and (Il) is oxygen can, however, also be joblained by dehydrogenative condensation of liydroxy- sgroup-terminated sulphonated polyethers with hydrogen siloxanes. Preferably the deliydrogenative condensation is carried out in the presence ofa catalyst, Suitable catalysts for the dehydrogenative condensation are, for example, NaOH, KOH, tetrmmethylammonium hydroxide, alkali metal fue. ides, alkaline earth metal fluorides, boron catalysts, such as ‘es(pentalluaropheny!)borane, carboxylic acids andior boxvlates or mixtures therwo, The eatalytie dehydrogenative condensation is desribed, for example, inthe specifications EP-A-1 460 098 (U.S. Pat. No. 7,053,166 B2, US-A 2004) 186259 Al), DE-A-108 12 636 (US-2004/186260 AT) and DE-A-108 59 764 (US-2005/136269 Al), inthe published application specification DE. 10 2005 0S1'939.3 (US-2087/ 100153 AL), and in the Japanese Patent Publication JP 448-1904], towhich US. Pat. No. 5,147,965 refers. Reference is expresiy made to the content of said specifications and the content of sid specifications forms part ofthe disclosure of the present application. [0142] 4 further possibilty for providing organosilicon compounds which fave units according 10 orrnula 1) whieh A is oxygen consists, for example, in adding com- pounds of the formula TSO,” L/W M** (see above for the ‘meaning of M) onto the double bond in aly sleoho!-staed polyedhers with OH terminus, Suh an addition is described, Tor example, in DE-C-36 33 421 (US. Pat. No. 4,927,961 A). Alternatively, polyethers with one silphonate terminus and ‘one OF termists can he prepared inthe manner described in the specification U.S. Pat. No. 3,823,185. Such OH-termi- tated polyethers can then, as describe above, be reacted by ‘dehydrogenative condensation with hydrogen silosanes. Kis likewise possible to fistly condense allyl alcohol started polyethers dehy crogenatively with hydrogen siloxanesand 10 ‘add compounds of the formula HSO,"/s M°* wo the double bond ofthe aly! group, 0143} It is also possible to wact hydrogen siloxanes with sulplonate-proup-containing and non-sulphonate-modified polyethers simultaneously or in any desired order [0144] Furthermore itis possible to add eompounds ofthe ormula HSO,” 1/v M™ only partially to polyethers with two alkenyl double boods andl 10. hydrsilylae the remaining double bonds with hydrogen siloxane, [0145] ‘The sulphonate-group-carying polyether used can be, for example, RALU®MER SPPE rom Raschig. This be prepared as described, for example, in lid-open speci cation DE-1 768 252 (U.S. Pt. No. 3.53117). Preferably, the polyether is prepared analogously to Example | of the Jaigkopen specification DE-1 768 282 (US, Pat. No. 3,531 4417) inthe way known tothe person skied inthe art. Flow ‘ever, neutralization is pariculely preferably’ not carried out asin Example I ofthe laid-open specification DE-1 768 252 (USS. Pat. No. 3,531,417) with concentrated hydrochloric acid, but with hydroxypropanesulphonic acid, which ean find its way into the subsequent reetion with the hydrogen silox- fe. The reaction of the allyl polyether with the propane sultone ean tke place in equimolar amounts or else using an excess of ally polyether orof propane sult. Ian excess of ally polyethers is sed, then the resulting mixturecan be usedUS 2008/0251751 AI directly in the hydrosilylation, To destroy any propane sul tone residues that may be present suitable additives, such as, Jor example, alcohols, alkoxides andor amines, can be use [0146] The present invention is described by way of ‘example in the examples given below, although the invention, the breadth of application of which arises from the overall ‘description and the claims, isnot intended to be restricted t0 the embodiments given inthe examples. EXAMPLES 110.4 Preparation of Onganositicon Compounds which have SiO Bond Fractions Drying of an Anionic Polyether: 10147] Uniess mentioned otherwise, the preduct RALLIRMER SPPE from Rasehig (polyethylene glycol aly (G-sulphopropyl dether potassium salt) was dred before the following reactions by azeotropic distillation with tolvene. Here, an approximately 70% strength by weight solution of the unionie polyether in oluene was oblained. The polyether ‘content was determined via the iodine number known to the person skilled in the ar. To destroy propane sllone residues, Trther additives ean be used in the azeotropic distilation, such as for example, sleohols, alkoxides andor amines EXAMPLE 1 Preparation by Hydeosilyiion [0148] 70.8 gofthe approximately 70% strength by weight solution of theanionie polyether in foluene obtained from the drying described above were initially introduced into 250 ri three-neck flask equipped with a stirer, a high-perfor- ‘mance condenser, a mushroom heating hood, a thermometer and dropping funnel, and heated to 50° C., and Karstedt catalyst. (platinum-divinyleyrumethyldsiloxane complex. from ABCR) was added sich that platinum was present inthe mixtureina conceatrationof S ppm based oa te otal mixture ‘weight, At 50° C., 15.0 g of 11,1,35,5.S-heptamethyhist- Joxane (Gelest) Were added. Further Karstet catalyst (10 ‘ppm by mass of platinum based on the total mixture weight) Was then added snd the mixtre was tiered fora further 3 hat 60 w 70° C. After removing the solvent under reduced pres- sure (membrane pump ‘cuum), a pale yellow, waxy-Hke solid was obtained whose Si-NMR spectrum (created sing Bruker AVANCE 400 NMR spectrometer with evaluation software XWIN-NMR 3.1 and tetramethylsilane as intemal standard revealed, inter alia, signals of the chemical shits of 19 ppm (units ofthe formula I where R=CH,,¢-3, R'=O—— (CH, —CH,—CH,—SO.Na; signal intensity 17% of the (CH),Si0 signals), -11 to ~12 ppm (units ofthe oma I where’ R-CH,, ¢-2, R'-O--CH, CH, CH, -SO,Na: signal intonsity 28% of the (CH,).8i0 signals), ~85 10 ~§9 Pm (uaits of the formula I where R-CH,, ¢-1, R'-O. CH, —CH,—-CH,SO,Na: signal intensity 22%% of the (CH) Si0 signals) and ~63 to -71 ppm (units ofthe formula Tere RCH, a1, b=O: signal intensity 35% ofthe (CH) .Si0 signals) EXAMPLE2 Preparation by Hydrosilylation [0149] 623g of the approximately 70% strength by weight Solution of the anionic polyether in toluene obtained from the drying described above were initially iatodveed ino 1 1 Oct. 16, 2008 thyceseck Has equipped with titer high-performan condenser, a mushroom beating hod, a Themometer and 8 eopping funnel, and heated to 7° C., and Kastdt exalt (Us ppm of platinum based onthe oll mixture weight) was andded At 70° C, 125 8 of 1,1 1,,8.5heptamethyisilox- fe were added. "The mixture Was then diluted with 47 g of toluene and tied fora farther 2h at 70°C. 39.7 of byl Aiglycot(iekylene glycol moncbutyl eer 299% Aldrich) ‘were added to 301 ofthe resulting reaction mixture andthe ‘olvent toluene wa removed under raced pressure (nem brane pump vaeum). Ths gavea pale brown, vseovs low~ able product whose “"S-NMR’spocirum’(eecorded a8 described in Example 1) exhibits, inter ai, signals ofthe chemical sills of 19 ppm (ants of the formula Il where RCH, ©=3, RIO. CH CH, CH SON signal intensity 11% of the (CH,),SiO signals), 11 10 =12 ppm {units ofthe formula Il where R-CHly,e-2, R'-O—CThy— CHi,~-Cil,S0,No: sina intensity 15% of the (CH S10 signals, -55 40 -59 ppm (units of the formula 11 where RCH, e-1, RO CH, CH,—CH,--SONNa: Signal intensity 19% of the (CH,).SiO signals and ~64 0 69 ppm (Units ofthe formula where R-CH,, a1, b-0: signa inten Si 20% ofthe (CH), Si0 signals). EXAMPLE 3 Preparation by Hydrosilyation [0180] 105 g of undried RALU®MER SPPE and 168 got nally aleobo-started polyethylene glycol of average molar ‘aks 400 g/mol were initially introduced ito 500 mal three neck flask equipped with a sire, a high-performance con- dense, a mushroom heating hood, a thermometer and adrop- Ping funnel, and bested to 70" C., and Karstodt catalyst (6 _Ppm by mass of platinum based on the total mixture weight) was aed. A170" C., 52 gol (CH),Si0—(Si(CH,),0) ,— (HSICH,O}, OSi (CH, (product of Goldschmidt GusbF) were added dropwise. Tie mixture was then stred for 2h at 707 C., further Karst catalyst (6 ppm by mass of platinum ‘based on the total mixture weight) was adced and the mixture ‘was steve fora frther 7h at 70° C.. pale yells, viscous pradict was obtained whose 'Si:NMR spectrum (obtained as deseribed in Example 1) exhibits, inter alia, signals of the ‘heiical shifts from ~20 to -23 pp (ons of the formula | where R=CH,, a=2, b-0; units of the formula Tt where ECHL, e=1, ACH, group, m=p-q-r-u-0, C=CH,CH.O, n>0, F-CH,CH,CH,; unit of the formula VIwhere R-CHs, scL.y-1,A-CH, group. m-p-q--u-0, C-CH_CH0, 10, L=H atom; signal intensity 18 times intensity of the (CH) {SiO signals) and ~58 to ~61 ppm (units ofthe formula VI ‘where R=CHy, x1, y=I, A=O atom, ‘formula Il where R-CH,, 61, R'-O—CH,—-CH, CH 'SO,Na: signal intensity 56% ofthe (CHL ),Si0 signa). EXAMPLE Preparation by Dehydrogenative Condensation [0151] Ina S00 ml tee-neck flask equipped witha sizer, high-performance condenser, mushroom heating hood, 3 thermometer anda dropping funnel, 110 zofa 70.1% strength by weight solution of an anionic polyether of the formula HO—{CH,CH,0),—-CH,CH,SO,Nawithanaverigemolar mass of 380 glinol, prepared according to the process described in the patent specification USS. Pat. No. 3,823,185,US 2008/0251751 AI were heated (© 120° C., and 2.5 mol %, based on the poly- ‘ether of 1:1 mixture (molar ratio) of laurie acc andeaesiu Taurate were added. At 120° C.. 40.7 gof 11,1,33,5,S:hep- tamethyltrsiloxane were added dropwise. The mintire was then sted for 3h at 120° C., and the solvent toluene was Oct. 16, 2008 jgnited and after a prebuming ime of 20, the extinguishing ‘Was started by pouring the foam generated directly hefore= ‘hand into the funnel. The results ae shown in Table 1, where in cach case the time in seconds until complete extinction Is given oensien crammsis Son ee : from Be removed unde recived pressure (membrane pimp vacim). AA pale yellow, wany-like product was obtained whose "Si NMR spectrum (records descrbod in Example 1) exhib- is, inter aia, signals ofthe chemical shifts from ~10 to =12 ‘pm (units ofthe formula I where R-CHy,¢-2, A~O atom, im=p-g--u-0, n>0, F=CH,CH: signal intensity 110% of the (CH, Si0 signa) EXAMPLES STO 10 Examples for Using the Organosticon Compounds Having SiC Bond Fractions 10152] The ability of the compounds according to the Invention t generate aqueous foams was tested by ascerain- fing the foaming number, The foaming number i Ue rato of the volume ofthe finished foam tothe volume of the wate! oan composition mixture. A detailed description of this parameter can be found, for example, in G. Rodewald, A. Rempe: “Feuerlischmittel. Bigensehatten— Wirkung—An- ‘wendung” [Fire-extingnishing compositions. Properties: effect— application}: Koblhammer Verlag. Stuttgart, 2005, For carrying out the test, the Power Blend MX 2080 stirer fom Braun was used, 100 ml of «solution of 0.45% by mass ‘of the surfactant tobe foamed and 1.0% by mass of the foam auxiliary butyl diglycol in tap water of about 10° German hardness were foamed for 30's and the volume ofthe foam ormed Was ascertained ia a measuring eylinder, The result ‘obtained are summarized in Table 1, the half-value time IVT I)being understood as meaning the time which elapses ‘until haf of the quid has reformed. Funermore, fresh foam tenerated in this way was used for extinguishing n-heptane fires in accordance with the general method described, for ‘example, in the laid-open spevtication DE-1 812 531. This, known tthe person skilled in heart that n-heptane isusedas ‘a defined model substance for engine fuel, in particular for Petrol. For this, analogously to the lac-open specification DE-2 240-263, a meal funnel witha funsel opening of 8am swat arranged over a metal dish with a diameter of 16 em, which contained 100 g of n-heptane. The n-heptane was [0153] Texapon NSO isa 27% strength by weight agueous sodium lauryl ether sulpate solution [C,sH.,-O-[(CH,) {—O}y-SO,INa from Cognis. {o1S4] With foaming numbers in the deliberately simply selected formulations inthe range from 3 t0 4 and half-valve ‘mes in the range from 4 1 5 min, the compounds secoeding to the invention aresuitableas foam compositions (Examples S108), [o1SS}_Ie is evident from Examples § to 10 thatthe foams ‘oblained from the compounds according to the invention are Suitable for extinguishing fuels. In particular, the formu les 1 and 2 (Examples 5 and 6) are perior to formulations containing non: conic surfactants (Fxample 9), EXAMPLES 11 0 13 Examples for Foam Stability [0186] The stability of the aqueous foams generated from the compounds according to the invention on hydrophobic Tiguids, as are encountered ia installations such a ol depos, pipes, pipelines or deums, when reducing evaporative losses ‘of volatile hydrocarbons or other onzanic solvents, nd when preventing thebreak-ontof fires, was ested on n-heptane For this, 15 ml of ncheptane were initially introduced into a Petri dish (121 em) and covered with foam whieh was obtained Irom in each ease 75 gof a I% strength aqueous solution by ‘foaming ina Elegant Feamer Line MS foam dispenser from Rexam Airspray. The time taken for the originally placed foam surface w half was measured (HVT 2). ‘The results jobiained are summarized in Table 2 TABLE 2 Hounsou eis pound (0% by Accolingto Branple $0) HVT 2 (ain _theimenton 1 fom eau 2 t=US 2008/0251751 AI 10157] The results in Table 2 show that the compounds soconding to the invention produce significantly more stable Joams on n-heptane than organic surfactants which ‘organosiicon compounds (Example 13) andar thus for generating aqueous foams avon hydrophobic liquids as ‘are encountered a instllaons such as oil depots, pipes, Pipelinesor drums, when rucing evaporative losses vola- tlebydrocarhons or olherorganie slventsand when prevent- ing the break-out of firs. 10188) Having thus described in detail various embodi- ‘ments ofthe present invention, iti to be understood that the ‘invention defined by the above paragraphs is otto be imited to particular details set forth in the above description as many ‘apparent variations thereof are possible without departing from the spirit or seope of the present invention, 1. Composition having organosilicon compounds for gen- ‘erating foams, characterized in that the composition com= prises one of more omganosilicon compounds which com prises 4) at least one siloxane unit ofthe formula (0) RLIRVO)SO raya ®, where Rand R are one or more identical or different radials independent of one another and selected from Tine for branched, saturated, mono- or polyunsaturated alkyl, haloalkyl, aryl, alkylary! or arylalkyl radicals having Ito 30 carbon atoms, where the radicals may ‘optionally be interupted by one or more oxygen and! ‘of nitrogen atoms andlor may optionally bavea OC (O}CH, group on the end of the radical, wis0, 1, 2or3 and xi80, 1.2083, ‘where the sum wx isnot greater than 3, ») optionally one or more siloxane wis of the general formula (V1) ERS, where Ris as R defined ina), ¥yis0, 1 or 2and Risa grup ofthe Formula A,-By-C-DyE-Ly where ais |, b,c,dandeareor I, = 0, ‘Asan oxygen atom, a CH, group ora CH=CH group, Bisa group ofthe general formula (HI1) ° I rit where _mis an integer from 0 10 30 and G may be a divalent group selected from linear or ‘branched, saturated, mono- or polyunsaturated alkyl aryl, alkylaryl oF arylalkyl groups having 1 w 20 ‘carbon atoms, Cis a CI, group or divalent radical selected from Tinear of branched, saturated, mono- oF polyuasatu a Oct. 16, 2008 rated alkyl, aryl, alkylaryl-oraryalhyl-oxy groups having Ito 20 carbon atoms ors group ofthe formals CH, 0— (CH), 0-5 Disa group ofthe general formula 1V) AC MLOUCHOY.C 8s OIC HO1— ww, where 1, p,q and rare integers from 0 to $0 independently of ‘one nother, anit more than one ofthe indices is, ‘4,200. the general formula (IV) isa random oligomer or ablock oligomer. isa group of the general formula (V) i Hoscnrof. where wis an integer from 0 to Sand {ifwis>0, may be identical or differen and is 3,4 0S nd [Lis selected from the group comprising hydrogen ‘atoms, linear or branched, saturated, mono- or poly- unsaturated alkyl, aryl aliylaryl or arylalkyl groups having 1 to 12 carbon atoms, acetoxy groups, POs, ‘aroups, POH 1M groups and PO 24M roups where Misa v-valeat cation Where vis 1,2,30r4,and «)at east one siloxane unit ofthe formula (1) which as at least one sulphonate group, FERS ssiye @, where RY isas RY defined under a) zis0, 1 or 2and Risa group of the formula AcBeC-Dekchy-SO/ 1A, where acandfare 1, band eare 0 oF 1 and lin at least 70% of the radicals R®1, where A.B,C,D,E and M" can have the meaning as given in by P isa divalent radical selected from linear or branched saturated, mono~or polyunsaturated alkyl, aryl, alky- lary] oraryalkyl groups having 1 1 20 carbon atoms ‘and IM isa vevalent cation where =I, 2,3 or 4, with the proviso that the radical i Sto 10D the radials ‘Asan oxygen atom and in0t0 95% ofthe radicals A isa CH, group andior a CH—CH group, 2. Composition cording 1 claim 1, characterized in that the ofganrilicon compounds having siloxane units of the formulae (1), (I) and optionally (VI) have,on average, a ratio of the number of silicon atoms tothe number of sulphonate aroups of fom 1.5:1 (02041 3. Composition according to elaim 2, characteriza in that ‘the onzanosilicon compounds have siloxane units of the for ‘mula (1) where RCH, and x-0 and siloxane units of the ormula (Il) where R°-CH,, 2-1, 2 0 3, Avoxygen atom oFUS 2008/0251751 AI group, m-0, C-CH, group or CH,CH,O group, toger from 0 020, p-q-r--Oand P=CH,CH, group o (CHCHLCH, group. 4. Composition coording to claim 2, characterized in that the oqganosilicon compounds have siloxane units ofthe for mula (2) where R'=CH, and x-0, siloxane units ofthe for mula (II) where R!=CH, A-oxygen stom or CH, group, m0, C-CH, group of CH,CH,O group, n and p-integers from 0 10 30 independently of one another, q-T-¥-0, F-CHCH, group or CH.CH,CH, group and siloxane unit ‘ofthe Formula (V1) where R°=CHy and y=1 of 2 5, Composition according to claim 2, charseterized in that the organosilicon compennds have, on average (0 (0 30 mol % of units ofthe formula (1) where R!=CH, ‘eroup, W=1, x-0, (0095 mol % of units ofthe formula (I) where R!-CH, ‘Broup, W-2,x-0, 00 70 mol % of units oF the formula (1) where R'“CH, BUP, WB, x0, (010 95 mol % of nits ofthe formula (1) where R°CHs group, 2-1, A-B-C—-CH, CH, CH, -O-, n<20, pard,F— CH ch, CH, (010 20 mol % of wits ofthe foemula (II) where R°=CH ‘group, 2-1, AO and BsC-D-E-T—SO, IW M CHCH, CH, SO, Law M™*, (010 20 mol % of wits ofthe formula (HI) where RICH, sgr0up, 2-2, A~O anid B-C-D-E-F—SO,” Li M™*—— CH.CH, CH, SO, Vw MO, (010 20 mol % of wits ofthe foemula (1) where RICH, 0p, 2-3, A~O and B-C-D-E-F—-SO.” I/w Mom (CH,CH,-CH,—SO, Liv M™, (040 30 mol % of units ofthe formula (V1) where R?=CH,, woup, ol, ABC CH, CH, CH, -O- rg r-t0-0, nspes0, C-CH,CHLO— or —CH (CHYCH.O— and Lis identical oF diferent and selected from the group consisting of CH, (CH) Clg, —(CH)sCHy, (CH) Clg, (CH). Gli, —cH-CH, and CCH cH, (040 30 mol Ya its ofthe formula (V1) where R?=CH, A-0, 1-0, n4pes0, rou, (C—CH,CH,O— or “CH(CH,)CH,O™ and L is identical or diffewent and selected from the group con- Sising of —CH,, —(CH,),CH,, —(CH,),CHy, {CH} CHy, —(CH),CHs, CH, —CH=CH, and cHACH-CH,, (010 30 mol % of its ofthe formula (V1) where R'=CH, ‘Erp, AO, meqrtwo, ntpeS0, (C—CHCHO— or “CH(CH,)CH,O™ and Lis identical or diffeent and selected from the group con= Siting of CH, —{CH,),CHy, —(CH,),CHy, {CH,},CHy, —(CH),CHs, CH, CH=CH and CH=CH CH, and (010 30 mol % of waits ofthe formula (V1) where RY-CH,, ‘0p, AO, meg-r-t-0, ntp<50, (C= CHCH,O— or“ CHICH,)CH,O" and Lis ‘entcal or different and selected from the group con Siting of —CHy, —(CH,),CHy, —(CH,),CHy, {CHL CH, — (CH,),CH, CH, CH=CH, and —cH_cncH,, 6. Composition eoording to cm 2, characterized in that Ain the sum of the siloxane units of the formula (I) and ‘optionally (V1) is oxygen to 75 to 75%. Oct. 16, 2008 7. Composition eeordi Ain the sum of the siloxane uni ‘optionally (Vis oxygen to 7.5 to 75%. '8. Composition ceording 1 claim 4, characterized in that A in the sum of the siloxane units ofthe formula (11) and ‘optionally (V2 is oxygen to 7.5 to 75%. 9. Composition aeeording 1 claim $, characterized in that Ain the sum of the siloxane units ofthe forma ([I) and ‘optionally (VI) is oxygen to 7.5 to 75%. 10, Composition according to claim I, characterized in that at least one of w and x is not zero 11. Composition aecording to clsim 2, charieterized in that at least one of w and x isnot zero 12, Composition aovording to claim 11, characterizedin ‘that Ain the sum ofthe siloxane units ofthe formula (I) and ‘optionally (VD is oxypen to 7.5 to 75% 13. A method of producing an aqueous foam which com- priws of 8) at least one siloxane uit ofthe formula (1) RLUROISI wae ©, where Rand R® are one or more identical or different radials independent of one another and selected fom linear ‘oF branched, saturated, mono- or polyunsaturated sky, haloalkyl, ary, alkylaryl or arylaky! radicals having 1 wo 30 carbon atoms, where the radicals may “optionally be interpted by one or more oxygen and ‘nitrogen atoms andor may optionally havea —OC (OKC, group on the end ofthe radical, wis0,1,2or3.and xis0, 1.2063, Where the stim Wx is not greater than 3, and ») optionally one or more siloxane unit formula (V1) BERS coins wn, of the general where R'is as Rt defined ina), yis0, 1 or2and Risa group of the formula A,-B,-C.-Dyl where ais, b,c. dandeare Or 1, His Vand aebscZ1, whore Asan oxygen atom, a CH group of a CH=CH group, Bisa group of the peneral formula (II) 4 where isan integer from 0 0 30 and G may be a divalent group selected from linear or branched, saturated, mono- or polyunsaturated alkyl ary, alkylary! or arylalky] groups having 1 « 20 ‘carbon atoms, Cis a Cll, group of a divalent radical selected from Tinear of branched, saturated, mon0- oF polyunsat= anUS 2008/0251751 AI tated alkyl, aryl alkylaryl- or arylalkyloxy groups having to 20 carbon atoms ora group ofthe fon CH1,—0—(CHi),—O- Disa group ofthe general formula (IV) (CHOWCHOYC HOYC0) ™, where 2, and ae integers from 0 10 50 independently of ‘one another, andif more than one of the indies isp. 4,100, the general formuls (IV) is random oligomer fr block oligomer, [Fis group ofthe general formula (V) ek where ‘isan integer fom 0 1 5 and {ifwis >0, may be identical or different and is3, 4 0S, and Lis selected from the group comprising hydrogen atoms, linear or branched, saturated, mono- or poly- ‘unsatrated alkyl, aryl, alkylary] oF arylalkyl groups having Ito 12 earbon atoms, acetoxy groups, POs, soups, PO4I 1/.M"™ groups and PO.” 2M ‘groups where Mi a vevalent cation where vis 1.2,30r4, with ©) atleast one siloxane unit ofthe formu (1) which ha a least one sulphonate group, RERSOjroasye ©, Oct. 16, 2008 where RY isas R! defined under a) 28 0,1 o¢ 2and Ris a group of the formula AeBeCeDy heh S05 1,N% where acandfare 1, band e are 0 oF Land «in at least 70% af the radicals R°1, where ‘A.B,C,D, Band M™ can have the meaning as given in be F isa divalent radical selected from linear or branched saturated, mono~ or polyunsaturated alkyl, aryl alky~ Jury] oraryllkyl groups having 1 1 20 carbon atoms and IM" is a vevalent cation where v-1, 2,3 oF 4, with the proviso that the radical in Sto 100% ofthe radicals ‘Asan oxygen atom and in 010 95% ofthe radicals A isa CH, group andlor a CA—CH group. 14, The method of clay 13 wherein the foam isa fre extinguishing foam or exercise foam 15, The method of elim 14 characterized in that surfae- tants with perfvorinated groups are added tothe mixture of ),¢) and optionally ), where the total content of surfactan ‘with perfaorinated groups is equal fo or les than half of foncenteation of surfactants with perflvorinated groups ‘eqired for generating an extinguishing foam without det able amounts of orzanoslicon compounds which have units ‘according to forma (1D, 16. The method of claim 13 wherein the foam for cleaning installations or apparatuses, for reducing evaporative losses or preventing the break-out of fires is produce.