EP0621057B1 - Emulgatoren für tragbare Feuerlöscher - Google Patents

Emulgatoren für tragbare Feuerlöscher Download PDF

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Publication number
EP0621057B1
EP0621057B1 EP19940400801 EP94400801A EP0621057B1 EP 0621057 B1 EP0621057 B1 EP 0621057B1 EP 19940400801 EP19940400801 EP 19940400801 EP 94400801 A EP94400801 A EP 94400801A EP 0621057 B1 EP0621057 B1 EP 0621057B1
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Prior art keywords
fluorinated
emulsifier according
emulsifier
integer ranging
carbon atoms
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EP19940400801
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English (en)
French (fr)
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EP0621057A1 (de
Inventor
Gilbert Garcia
Elisabeth Morillon
Christian Varescon
Casimir Kalinka
Ivan Devaux
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EIDP Inc
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Elf Atochem SA
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Classifications

    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
    • A62D1/0071—Foams
    • A62D1/0085—Foams containing perfluoroalkyl-terminated surfactant

Definitions

  • the present invention relates to the field of fire extinguishing and more particularly relates to foam concentrates for portable water spray extinguishers.
  • foaming base generally consists of a hydrolyzate of animal proteins (hair, horns, hooves, hemoglobin).
  • fluorosurfactants to obtain a fluoroprotein foam concentrate; such emulsifiers are described, for example, in patents GB 1,280,508, GB 1,368,463, US 4,424,133, EP 49,958, US 4,460,480, FR 2,230,384, GB 2,011,784 and WO 8803425.
  • the foaming base is composed of a mixture of hydrocarbon-based surfactants.
  • Film-forming fluorinated surfactants can also be incorporated.
  • AFFF foam concentrates the presence of the fluorinated surfactant makes it possible to produce a foam which, by decantation, forms an aqueous film floating above the surface of the hydrocarbon. The purpose of this aqueous film is not only to extinguish the fire, but also to prevent a possible re-ignition of the surface of the hydrocarbon.
  • Foam concentrates of this type have been described in numerous patents, in particular the following: GB 1 258 299, US 5 085 786, FR 2 347 426, US 3 957 657, FR 2 040 316, US 4 350 206, FR 3 562 156, FR 2 148 442, FR 2 407 724, FR 2 385 413, US 3 772 195, FR 2 397 847, US 3 661 776, US 3 839 425, FR 2 103 669, US 3 957 657, US 3 963,776 and FR 2,296,625.
  • the spreading coefficient must be positive, care must be taken that the interfacial tension ( ⁇ i ) is not too low in order to avoid emulsification of the hydrocarbon by the extinguishing composition or too great a thinning of the aqueous film.
  • the emulsification of the hydrocarbon by the extinguishing composition risks in fact causing the entrainment of part of the hydrocarbon inside the extinguishing foam, of contaminating the latter and of igniting it.
  • the thermal resistance of the aqueous film Another important factor vis-à-vis the re-ignition phenomenon is the thermal resistance of the aqueous film.
  • an excessive spreading speed leads to the formation of a very thin film which is not very resistant to heat; conversely, the films most resistant to heat are those with the slowest speed of formation. It is therefore important to find a compromise between the spreading speed and the thermal resistance of the aqueous film, this property being essential for obtaining good resistance to re-ignition.
  • the aqueous film which removes the hydrocarbon vapors can at any time, for example by stirring, be separated from the foam from which it comes and be found directly in contact with an ignited part. If its thermal resistance is too low, the film can be destroyed and release hydrocarbon vapors which ignite immediately and continue to destroy the rest of the film.
  • AFFF foam concentrates which are generally used with fire hoses are not suitable in a portable extinguisher designed to be carried and used by hand and which, in working order, has a mass less than or equal to 20 kg.
  • the amount of water available to dilute the foam concentrate to the use concentration (0.5 to 6%, most often 1 to 3%) is limited and generally set at 6 or 9 liters , while in the application system by means of a lance the quantity of water available is not limited. Therefore, to meet the certification standards for foaming liquids for hydrocarbon fires, an emulsifier for portable extinguisher must be much more efficient than a conventional emulsifier for fire hoses.
  • the portable extinguisher must extinguish with only 6 liters of foam concentrate solution diluted to 3% (French standard) S61-900), while in the case of extinction with a fire hose the maximum available quantity of foam concentrate solution diluted to 3% may be up to 28.5 liters (French standard S60-220) or 22 , 3 liters (UL 162 standard).
  • the non-fluorinated surfactant (d) can be chosen from the compounds of the following formulas: R 4 -OSO 3 M (IV-1) R 4 - (OC 2 H 4 ) r -OSO 3 M (IV-2) R 4 (OC 2 H 4 ) r -OH (IV-3) R 4 -CONH-C 2 H 4 -NH-C 2 H 4 OC 2 H 4 COOM '(IV-6) R 4 -NH-C 2 H 4 -COOH (IV-7) R 4 -N (C 2 H 4 COOM ') 2 (IV-8) R 4 -CONH-C 3 H 6 -N ⁇ (CH 3 ) 2 CH 2 COO ⁇ (IV-10) R 4 -N (CH 3 ) 2 ⁇ O in which R 4 represents an alkyl radical, linear or branched, containing from 8 to 18 carbon atoms, r is an integer ranging from 1 to 16, M denotes an alkali metal ion or
  • monoalkyl ethers there may be mentioned the monoethyl or monobutyl ether of ethylene glycol and the monobutyl ether of diethylene glycol, the latter being preferred.
  • the foam concentrates according to the invention can be prepared by simple mixing of the various constituents until homogenization. To accelerate homogenization, one can operate by heating to a temperature between room temperature and that of boiling of the mixture, preferably at a temperature between 30 and 60 ° C.
  • the pH of the foam concentrate is advantageously stabilized at a value at least equal to 7 (preferably between 8 and 10) by means of a weak base, for example ammonia or an organic base such as diethanolamine, triethanolamine, urea.
  • a weak base for example ammonia or an organic base such as diethanolamine, triethanolamine, urea.
  • the foam concentrates according to the invention can be used in a portable fire extinguisher in an amount of 0.5 to 6 parts by weight (preferably 1 to 3 parts) of foam concentrate per 100 parts by weight of water.
  • This test which indicates the speed of formation of the aqueous film on the surface of the hydrocarbon, is carried out by pouring 50 ml of hydrocarbon (heptane) into a Petri dish (diameter: 11.5 cm), the outer face of which is painted in black so that you can watch the film.
  • hydrocarbon heptane
  • Petri dish diameter: 11.5 cm
  • 0.1 ml of a 3% aqueous emulsifier solution is deposited using a micropipette.
  • the solution should be applied dropwise starting from the center and making an eccentric movement.
  • the stopwatch is started when the first drop is deposited and stopped when the film has covered the entire surface of the hydrocarbon. We note the time. If the total recovery is not obtained in less than a minute, the percentage of surface covered after one minute is noted.
  • the spreading is satisfactory if the total recovery is obtained in less than 30 seconds, preferably between 5 and 25 seconds.
  • the evaluation of the thermal resistance of the aqueous film is obtained by measuring the Limit Temperature of Film Stability (TLSF).
  • TLSF Limit Temperature of Film Stability
  • a good foam concentrate should lead to a TLSF higher than 35 ° C, preferably higher than around 40 ° C
  • the expansion is the ratio of the volume of foam produced from a 3% aqueous solution of foam concentrate to the initial volume.
  • 100 ml of 3% aqueous emulsifier solution is introduced into a 1 liter test tube, then the solution is beaten for one minute at the rate of one beat per second using a perforated circular piston (30 holes of 5 mm in diameter representing 25% of the surface) and fixed in its center to a metal rod.
  • a satisfactory foam concentrate must lead to an expansion at least equal to 8.
  • the surface tension ( ⁇ s ) with tap water and the interfacial tension ( ⁇ i ) with heptane are measured using a LAUDA tensiometer in accordance with ISO 304 and ISO 6889, but operating at 25 ° C .
  • B fluorinated amine oxide of formula: C 6 F 13 -CH 2 CH 2 -SO 2 NH-CH 2 CH 2 CH 2 -N (CH 3 ) 2 ⁇ 0 marketed by the Applicant in the form of a 40% hydroalcoholic solution.
  • C Alkyl (C 8 and C 10 ) -glucoside sold in the form of a 70% aqueous solution by the company UNION CARBIDE under the name Triton BG 10.
  • D3 Alkyl (C 12 and C 14 ) -amidopropylbetaine of formula: Alkyl-CONH-CH 2 CH 2 CH 2 -N ⁇ (CH 3 ) 2 CH 2 COO ⁇ sold in 30% aqueous solution under the name Ampho-tensid B4 by the company ZSCHIMMER and SCHWARTZ.
  • D4 Decyl ether sulfate of formula: C 10 H 21 (OC 2 H 4 ) 2 OSO 3 Na used in 30% aqueous solution.
  • E Mono-n.butyl ether of diethylene glycol: C 4 H 9 OC 2 H 4 -OC 2 H 4 OH
  • an emulsifier according to the invention is prepared, the active ingredient contents of which are as follows: Constituents Content (% ) AT 10.8 B 6.2 VS 3.3 D1 7.9 E 40.0 ethanol 5.4 water (qs 100%) 26.4
  • This composition brought to pH 9.3 by addition of diethanolamine, has the following characteristics: - freezing temperature -22 ⁇ 2 ° C - Volumic mass 1.065 - viscosity 18 mPa.s - refractive index 1,414 - ⁇ s (3% city water) 16.4 mN / m - ⁇ i (3% city water / heptane) 2.5 mN / m - flash point (in closed section) 50 ° C
  • this foam concentrate leads to the following performances: - spreading 20 seconds - TLSF 47 ° C - profusion 10.2 90 ml of this foam concentrate
  • the foam concentrates (b1) and (b2) prove to be less efficient than the foam concentrate of example 1-a.
  • Example 1-a is repeated, but the proportions of the various constituents are modified and / or the surfactant D1 is replaced by the compound D2.
  • Example 1-a The procedure is as in Example 1-a, but a part of the ether E is replaced by monoethylene glycol (hereinafter MEG) and the proportions of the various surfactants are varied.
  • MEG monoethylene glycol
  • Example 1-a The procedure is as in Example 1-a, but a part of the ether E is replaced by monoethylene glycol and at least one of the surfactants D2, D3 and D4 is used in place of D1 and / or instead of alkylglucoside C.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Business, Economics & Management (AREA)
  • Emergency Management (AREA)
  • Fire-Extinguishing Compositions (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)

Claims (12)

  1. Emulgator für tragbare Feuerlöscher, dadurch gekennzeichnet, daß er aus einer wäßrigen Lösung besteht, die in Gewichtsprozent enthält:
    (a) 1 bis 15 % mindestens eines fluorierten Betains der allgemeinen Formel
    Figure imgb0026
     in der Rf einen linearen oder verzweigten Perfluoralkylrest mit mindestens 6 Kohlenstoffatomen darstellt, m eine ganze Zahl von 0 bis 6 ist, X eine Gruppe CO oder SO2 darstellt, R ein Wasserstoffatom oder ein Methyl- oder Ethylrest ist, n eine ganze Zahl von 1 bis 5 darstellt, R1 und R2, identisch oder verschieden, jeweils einen Methyl- oder Ethylrest darstellen, p eine ganze Zahl von 1 bis 5 ist und Y- eine Gruppierung SO3 -, OSO3 - oder COO- darstellt;
    (b) 1 bis 20 % mindestens eines fluorierten Aminoxids der allgemeinen Formel
    Figure imgb0027
     in der die Symbole RF, m', n', X', R', R1' und R2' jeweils dieselbe allgemeine Bedeutung wie Rf, m, n, X, R, R1 bzw. R2 haben;
    (c) 2 bis 8 % mindestens eines Alkylglucosids der allgemeinen Formel

            H(C6H10O5)qOR3     (III)

    in der q eine ganze Zahl von 1 bis 6 darstellt und R3 einen Alkylrest, linear oder verzweigt, mit 6 bis 18 Kohlenstoffen bedeutet;
    (d) 2 bis 10 % mindestens eines anionischen, nichtionischen oder amphoteren oberflächenaktiven Mittels, das sich von denen der Formel III unterscheidet;
    (e) 20 bis 50 % mindestens eines Monoalkylethers von Mono- oder Diethylen(oder -propylen)glykol;
    der Gesamtgehalt an fluorierten Verbindungen a und b liegt zwischen 5 und 25 %, und das Gewichtsverhältnis ( a + b )/( c + d
    Figure imgb0028
    ) liegt zwischen 1 und 2.
  2. Emulgator nach Anspruch 1, dadurch gekennzeichnet, daß er 2 bis 12 % fluorierte(s) Betain(e), 3 bis 15 % fluorierte(s) Aminoxid(e), 3 bis 6 % Alkylglucosid(e), 3 bis 8 % eines oder mehrerer sich von der Formel III unterscheidender oberflächenaktiver Mittel und 30 bis 45 % Monoalkylether von Mono- oder Diethylen(oder -propylen)glykol enthält.
  3. Emulgator nach Anspruch 1 oder 2, bei dem der Gesamtgehalt an fluorierten Verbindungen zwischen 7 und 18 % beträgt.
  4. Emulgator nach einem der Ansprüche 1 bis 3, in dem das Gewichtsverhältnis ( a + b )/( c + d
    Figure imgb0029
    ) zwischen 1,3 und 1,7 liegt.
  5. Emulgator nach einem der Ansprüche 1 bis 4, bei dem die Reste Rf und/oder RF 6 bis 16 Kohlenstoffatome enthalten, m und/oder m' gleich 0 oder 2 betragen, n und/oder n' gleich 3 sind, p gleich 1 oder 2 ist, q gleich 1 oder 2 ist und der Rest R3 8 bis 14 Kohlenstoffatome enthält.
  6. Emulgator nach Anspruch 5, enthaltend eine Mischung fluorierter Betaine der Formel

            CxF2x+1CH2CH2-SO2NH-CH2CH2CH2-N⊕(CH3)2CH2COO⊖

    in der x eine gerade ganze Zahl von 6 bis 16 ist und der Gehalt der Mischung an Betain mit einem C6F13-Rest mindestens 50 Gew.-% beträgt.
  7. Emulgator nach Anspruch 5 oder 6, bei dem das Aminoxid die Verbindung C 6 F 13 -CH 2 CH 2 -SO 2 NH-CH 2 CH 2 CH 2 -N(CH 3 ) 2 →O
    Figure imgb0030
    ist.
  8. Emulgator nach einem der Ansprüche 1 bis 7, bei denen das nichtfluorierte oberflächenaktive Mittel (d) aus den Verbindungen der folgenden Formeln ausgewählt ist:

            R4-OSO3M     (IV-1)



            R4-(OC2H4)r-OSO3M     (IV-2)



            R4(OC2H4)r-OH     (IV-3)

    Figure imgb0031

            R4-CONH-C2H4-NH-C2H4OC2H4COOM'     (IV-6)



            R4-NH-C2H4-COOH     (IV-7)



            R4-N(C2H4COOM')2     (IV-8)

    Figure imgb0032

            R4-CONH-C3H6-N⊕(CH3)2CH2COO⊖     (IV-10)

    R 4 -N(CH 3 ) 2 →O
    Figure imgb0033
     in denen R4 einen Alkylrest, linear oder verzweigt, mit 8 bis 18 Kohlenstoffatomen darstellt, r eine ganze Zahl zwischen 1 bis 16 ist, M ein Alkalimetall- oder quaternäres Ammoniumion bezeichnet und M' ein Alkalimetallion bezeichnet.
  9. Emulgator nach einem der Ansprüche 1 bis 8, bei dem der Ether (e) der Monobutylether von Diethylenglykol ist.
  10. Emulgator nach einem der Ansprüche 1 bis 9, stabilisiert bei einem pH-Wert von mindestens 7, vorzugsweise zwischen 8 und 10.
  11. Emulgator nach einem der Ansprüche 1 bis 10, weiterhin enthaltend ein alkoholisches Co-Lösemittel, ein Antigel, ein Konservierungsmittel und/oder ein korrosionsverhinderndes Mittel.
  12. Verwendung eines Emulgators nach einem der Ansprüche 1 bis 11 in einem tragbaren Feuerlöscher in Mengen von 0,5 bis 6 Gew.-Teilen, vorzugsweise 1 bis 3 Gew.-Teilen, des Emulgators auf 100 Gew.-Teile Wasser.
EP19940400801 1993-04-23 1994-04-13 Emulgatoren für tragbare Feuerlöscher Expired - Lifetime EP0621057B1 (de)

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FR9304821 1993-04-23
FR9304821 1993-04-23

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EP0621057B1 true EP0621057B1 (de) 1996-11-13

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EP (1) EP0621057B1 (de)
JP (1) JP2575289B2 (de)
AU (1) AU658341B2 (de)
CA (1) CA2121654A1 (de)
DE (1) DE69400885T2 (de)
DK (1) DK0621057T3 (de)
ES (1) ES2094028T3 (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101358249B1 (ko) 2013-07-19 2014-02-06 혜정산업 (주) 친환경 수성막포소화약제 조성물
KR101366308B1 (ko) 2013-07-19 2014-02-21 혜정산업 (주) 친환경 포소화약제 조성물

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0726792A4 (de) * 1993-11-01 1997-03-19 Tyler Robert E Feuerbekämpfende und kühlende schaumzusammensetzung
FR2734737B1 (fr) * 1995-06-01 1997-07-11 Seppic Sa Composition moussante et son utilisation comme emulseur anti-incendie
AU2830997A (en) * 1996-06-06 1998-01-05 Minnesota Mining And Manufacturing Company Fire-fighting agents containing adsorbable fluorocarbon surfactants
KR20010032921A (ko) * 1997-12-10 2001-04-25 스프레이그 로버트 월터 흡착성 플루오로카본 계면활성제를 포함하는 소화제
US6379578B1 (en) 1998-08-14 2002-04-30 Gtl Co., Ltd. Water-based foam fire extinguisher
JP3377450B2 (ja) * 1998-08-14 2003-02-17 株式会社ジー・ティ・エル 水系泡消火剤
FR2787721B1 (fr) * 1998-12-24 2001-02-02 Atochem Elf Sa Compositions extinctrices
EP2224802A2 (de) * 2007-12-21 2010-09-08 Cognis IP Management GmbH Adjuvanzien für agrochemische anwendungen
NZ609760A (en) * 2010-10-01 2015-08-28 Tyco Fire Products Lp Aqueous fire-fighting foams with reduced fluorine content
BE1025603B1 (fr) * 2018-02-06 2019-04-25 Uniteq S.A. Composition de mousse extinctrice
TW202035361A (zh) * 2018-12-12 2020-10-01 美商3M新設資產公司 氟化胺氧化物界面活性劑
CN110478847B (zh) * 2019-09-29 2021-08-13 中国科学技术大学 一种基于短链氟碳的环保型水成膜泡沫灭火剂

Family Cites Families (3)

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US4090967A (en) * 1975-12-19 1978-05-23 Ciba-Geigy Corporation Aqueous wetting and film forming compositions
DE2732555C2 (de) * 1977-07-19 1982-07-01 Hoechst Ag, 6000 Frankfurt Fettalkoholfreies Schaumlöschkonzentrat
US4999119A (en) * 1989-07-20 1991-03-12 Chubb National Foam, Inc. Alcohol resistant aqueous film forming firefighting foam

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101358249B1 (ko) 2013-07-19 2014-02-06 혜정산업 (주) 친환경 수성막포소화약제 조성물
KR101366308B1 (ko) 2013-07-19 2014-02-21 혜정산업 (주) 친환경 포소화약제 조성물

Also Published As

Publication number Publication date
JP2575289B2 (ja) 1997-01-22
DK0621057T3 (da) 1997-04-28
ES2094028T3 (es) 1997-01-01
DE69400885T2 (de) 1997-05-15
AU6059594A (en) 1994-11-17
CA2121654A1 (fr) 1994-10-24
EP0621057A1 (de) 1994-10-26
JPH06312030A (ja) 1994-11-08
AU658341B2 (en) 1995-04-06
DE69400885D1 (de) 1996-12-19

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