EP0755701B1 - Polyvalenter, filmbildender Fluoroproteinemulgator - Google Patents

Polyvalenter, filmbildender Fluoroproteinemulgator Download PDF

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Publication number
EP0755701B1
EP0755701B1 EP96401470A EP96401470A EP0755701B1 EP 0755701 B1 EP0755701 B1 EP 0755701B1 EP 96401470 A EP96401470 A EP 96401470A EP 96401470 A EP96401470 A EP 96401470A EP 0755701 B1 EP0755701 B1 EP 0755701B1
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denotes
emulsifier according
fluorinated
equal
hydrogen atom
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French (fr)
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EP0755701A1 (de
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Gilbert Garcia
Pierre Durual
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Arkema France SA
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Elf Atochem SA
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    • 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 extinguishing fires and more particularly for the purpose of multipurpose film-forming fluoroprotein fire-fighting foam concentrates, that is to say usable both on hydrocarbon fires and on polar liquid fires.
  • Fire-fighting foam concentrates are an effective means of fighting fires of combustible liquids. When in use, they are diluted in water from city water or seawater, generally at a volume concentration of 3% (i.e. 3 volumes of foam concentrate for 97 volumes of water) or 6% (6 volumes of foam concentrate for 94 volumes of water).
  • 3% i.e. 3 volumes of foam concentrate for 97 volumes of water
  • 6% 6 volumes of foam concentrate for 94 volumes of water.
  • the amount of active ingredients needed to satisfy with the minimum extinguishing performance required being identical in both cases of dilution, the emulsifiers dilutable to 3% are therefore at least twice as concentrated than those that can be diluted to 6%; they allow users to store quantities lower foam concentrates, save space and reduce storage costs.
  • the resulting mixture After dilution with water of the foam concentrate, the resulting mixture produces a foam aqueous by incorporation of air and supply of mechanical energy by means of a lance fire-fighting or any other foam generator. This foam is spilled on fires of combustible liquids and acts by smothering and cooling to total extinction.
  • foaming base consists of a animal protein hydrolyzate to which fluorinated surfactants are added and foam stabilizing solvents.
  • foam stabilizing solvents are described for example in patents GB 1,280,508, GB 1,368,463, US 4,424,133, FR 2,230,384, WO 8803425 and US 3,475,333.
  • Fluoroprotein foam concentrates such as those described above do not cannot be used for extinguishing fires of polar liquids (alcohols, ketones, esters or ethers).
  • polar liquids alcohols, ketones, esters or ethers.
  • the preparation and use of such emulsifiers containing a polysaccharide as an alcoophobic agent are described in US Patents 4,149,599, US 4,464,267, FR 2,206,958 and WO 9215371.
  • the polysaccharide contained in the foam precipitates on contact with polar liquid and forms a protective gelatinous sheet which insulates the foam against the destructive action of the polar liquid.
  • the foam can then spread over the sheet gelatinous and turn off the heat.
  • the polysaccharide in solution aqueous being a viscosifying macromolecule, it considerably increases the final viscosity of the foam concentrate, which causes pumpability problems in the injection and dilution systems, especially in the cold.
  • Patent EP 595,772 is described the association of a polysaccharide with an anionic hydrophilic polymer making it possible to prepare solutions of low viscosity.
  • Patent EP 609 827 which describes the association of a polysaccharide and of an alginate, indicates the means of reducing the viscosity of a polyvalent foam concentrate by controlling the relative proportions of the polysaccharide and the alginate; the viscosity can also be reduced by controlling the salt concentration ratio aryl- or alkylaryl-sulfonic acid at the concentration of other hydrocarbon surfactants.
  • Patents FR 2 636 334 and FR 2 637 506 describe the chemical modification polysaccharides by grafting perfluoroalkyl groups on the Hydrophilic side chains of the polysaccharide.
  • the presence of perfluoroalkyl radicals increases the alcoophobic character of the polysaccharide and improves its efficiency forming an insoluble gel on the surface of the polar solvent; this allows to reduce the polysaccharide content and therefore the final viscosity of the foam concentrate.
  • this chemical grafting reaction requires heating to 50-70 ° C for two o'clock.
  • Patent EP 524 138 relates to versatile foam concentrates combining a polysaccharide with a fluorinated co-telomer.
  • the fluorinated co-telomer is obtained by radical telomerization of a fluorinated telogen on a mixture of acrylic monomers or non-fluorinated methacrylics.
  • the association of the co-telomer with the polysaccharide enhances its efficiency and allows the incorporation of lower quantities, therefore obtaining versatile, less viscous foam concentrates.
  • the emulsifiers described above do not retain any minus a pseudoplastic character whose viscosity varies with the shear rate.
  • foam concentrates based on hydrolyzed proteins often contain iron in the form of ferrous chloride or sulfate which, in some cases, pose compatibility problems with polysaccharides and cause some deposit.
  • emulsifiers including the combination of a protein hydrolyzed with a metallic soap dissolved in a amino alcohol.
  • foam concentrates have the disadvantage of having to be used very quickly after dilution with water because they precipitate at the time of dilution; in in addition, this type of product gives rise to significant sedimentation during storage.
  • fluorinated telomeres as oleophobic agents in fluoroprotein emulsifiers is known and described in particular in patents EP 19584 and FR 2,575,165. These fluorinated telomeres with hydrophilic side chain improve foam expansion, mobility and resistance to contamination by hydrocarbons; the same is true in US Pat. No. 4,460,480 which describes the use fluorinated co-telomeres for the same application. However, the use of such foam concentrates for extinguishing polar liquid fires are neither described nor suggested in these patents.
  • the present invention aims to overcome all the problems associated with the use of polysaccharides and to obtain film-forming fluoroprotein emulsifiers versatile, i.e. usable both on hydrocarbon fires and on fires of polar liquids, and having a rheological profile of the Newtonian fluid type, that is, their viscosity is independent of the shear rate of so as to facilitate their flow in the injection and dilution systems at time of use.
  • non-fluorinated protein foaming base with (a) at least one co-telomer fluorinated having a perfluoroalkyl radical and a polymerized chain consisting units of an anionic hydrophilic monomer and a nonionic hydrophilic monomer and (b) at least one fluorinated surfactant including an aqueous solution at 1 g / l has a surface tension of less than 25 mN / m.
  • the foam concentrates thus formed are effective against both hydrocarbon and fire fires polar liquids. Containing no high weight thixotropic hydrophilic polymer molecular type polysaccharide, they are perfectly fluid even at low temperature.
  • Protein hydrolysates which consist mainly of water and soluble oligomers of hydrolyzed proteins, the dry extract of which is usually about 20 to 50% by weight, are well known products (see for example US Patents 2,361,057 and US 4,424,133). They are generally obtained by hydrolysis of animal proteins such as, for example, the keratin contained in hooves, hair, feathers and horns, or albumin in the blood animals. These organic materials are treated hot, possibly under pressure, by an alkaline solution (soda or lime) and the liquid resulting from the hydrolysis is neutralized at a pH between 5 and 9 (preferably between 6 and 8), filtered and concentrated. Before storage, a fermentation inhibitor is generally added thereto such as formalin and various mineral additives such as salts of iron, zinc, calcium or magnesium.
  • the protein hydrolyzate serves as a diluting medium for components (a) and (b) of the foam concentrate according to the invention.
  • the weight content of co-telomer (s) fluorinated (s) is advantageously between 0.1 and 5%, preferably between 0.5 and 2%. That of fluorinated surfactant (s) can range from 0.5 to 10% and is preferably between 1 and 5%.
  • co-telomeres those in which k is equal to 0 or 2, X represents the group OCO, n is equal to 0 or 1, the sum q 1 + q 2 is between 10 and 50 , Y is a hydrogen or iodine atom, M 1 is a unit of formula: and M 2 a unit of formula: in which R and R ′, which may be identical or different, each represent a hydrogen atom or a methyl radical, Q 1 represents a hydrogen atom, an alkali metal ion or a quaternary ammonium ion, and Q 2 represents an OH group or a group CONR 1 R 2 in which the symbols R 1 and R 2 , identical or different, each represent a hydrogen atom or an alkyl or hydroxyalkyl radical containing from 1 to 3 carbon atoms.
  • a solvent chosen from the alcohols (preferably methanol, ethanol, isopropanol or tert-butanol) and glycol ethers, especially glymes (preferably mono and diglyme).
  • alcohols preferably methanol, ethanol, isopropanol or tert-butanol
  • glycol ethers especially glymes (preferably mono and diglyme).
  • the radical initiator can be an azo type initiator such as, for example, azo-bis-isobutyronitrile or 4,4'-azo-bis-cyanopentanoic acid, or a peroxide type such as, for example, dicyclohexyl peroxy di-carbonate, benzoyl peroxide or di-tert-butyl peroxide.
  • the initiator can be used in solution and in this case use the reaction solvent or methylene chloride or N-methyl pyrrolidone.
  • the concentration of the initiator can vary from 0.5 to 25% by weight relative to the telogen depending on the relative reactivity of the telogen and of the monomers M 1 and M 2 .
  • the reaction temperature is between 0 and 150 ° C, preferably between 60 and 90 ° C.
  • acrylic acid and its alkali metal salts are preferred.
  • acrylamide or vinyl acetate are preferred.
  • co-telomeres can also take place in two stages comprising a stage of telomerization of a single non-ionic hydrophilic monomer of type M 2 , followed by a partial hydrolysis transforming a fraction of the units M 2 into units of hydrophilic monomer anionic type M 1 .
  • a stage of telomerization of a single non-ionic hydrophilic monomer of type M 2 followed by a partial hydrolysis transforming a fraction of the units M 2 into units of hydrophilic monomer anionic type M 1 .
  • the surfactant (s) to be used according to the invention can be chosen, without limitation, from the compounds of formulas: Rf - (CH 2 ) w - S - (CH 2 ) t - CONH - C (CH 3 ) 2 -CH 2 SO 3 Na in which Rf represents a linear or branched perfluoroalkyl radical containing at least 6 carbon atoms, s is an integer ranging from 0 to 6, R 6 represents a hydrogen atom or a methyl or ethyl radical, t and u are whole numbers ranging from 1 to 5, v is equal to 2 or 3, the symbols R 7 , R 8 and R 9 , identical or different, each represent a methyl or ethyl radical, and w is an integer ranging from 1 to 6.
  • fluorinated surfactants (b) which can be used in the context of the invention, there may be mentioned more particularly the compounds of formulas: C 6 F 13 - CH 2 CH 2 - SO 2 NH- CH 2 CH 2 - N ⁇ (CH 3 ) 2 - CH 2 - COO ⁇ C 6 F 13 - CH 2 CH 2 - SO 2 NH - CH 2 CH 2 CH 2 - N ⁇ (CH 3 ) 2 - CH 2 - COO ⁇ C 8 F 17 - SO 2 NH - CH 2 CH 2 CH 2 - N ⁇ (CH 3 ) 2 - CH 2 - COO ⁇ C 6 F 13 - CH 2 CH 2 - SO 2 NH - CH 2 CH 2 CH 2 - N ⁇ (CH 3 ) 2 - CH 2 CH 2 - COO ⁇ C 6 F 13 - CH 2 CH 2 - SO 2 NH - CH 2 CH 2 CH 2 - N ⁇ (CH 3 ) 2 - CH 2 CH 2 - COO ⁇ C
  • the preparation of the foam concentrates according to the invention can be carried out by simple addition to the hydrolyzate of proteins of constituents (a), (b) and any additives.
  • the operation can be performed at room temperature or by heating to a moderate temperature, with stirring.
  • the fluoroprotein foam concentrate thus obtained can be diluted with city water or sea water at a rate of 0.5 to 6 parts by volume (from preferably 1 to 3 parts by volume) for 100 parts by volume in total.
  • the composition resulting fire extinguisher is used to fight oil fires and of polar liquids.
  • the expansion is the ratio of the volume of foam produced from a 3% aqueous solution of foam concentrate by volume of initial liquid.
  • the expansion should be at least 6.
  • the drainage time should be between 5 and 20 minutes.
  • This test which indicates the rate of formation of the aqueous film on the surface of the hydrocarbons, is made by pouring 50 ml of hydrocarbon into a Petri dish (diameter: 11.8 cm) whose outer face is painted black in order to be able to observe the film.
  • a Petri dish diameter: 11.8 cm
  • the stopwatch is started at the time of filing the first drop and stopped when the film has covered the entire surface of the oil. We note the time. If the total recovery is not obtained in less than a minute, we note the percentage of surface covered after one minute.
  • the most efficient foam concentrates to give waterproof foam to polar liquid vapors are those with the lowest evaporation in mg / min.
  • Tests are also carried out under more severe conditions on polar liquid.
  • the procedure is identical but the liquid is ignited polar and let it burn for 90 seconds before pouring out the foam to turn it off.
  • the quantity of polar liquid used is 150 ml and approximately 50 g of foam.
  • the acetone evaporation rate must be less than 85 mg / min for the cold test and less than 150 mg / min for the fire test.
  • Rf 1 , Rf 2 , Rf 3 , Rf 4 , Rf 5 and Rf 6 each represent a mixture of linear perfluoroalkyl radicals.
  • the relative proportions of the various perfluoroalkyl radicals in% by mass in the mixtures designated Rf 1 , Rf 2 , Rf 3 , Rf 4 , Rf 5 and Rf 6 are indicated in the following table.
  • the dry extracts were determined by keeping the oven for 5 hours at 120 ° C 10 to 20 g of solution placed in a crystallizer of 150 mm in diameter.
  • a fluoroprotein foam concentrate according to the invention is obtained.
  • This foam concentrate is diluted to 3% with city water and with synthetic sea water and the two resulting solutions, subjected to the tests described above, have the characteristics given in the following table.
  • Feature Dilution with city water Dilution with synthetic seawater Spreading 8.5 9.0 Drainage time at 25% 9 min 30 s 9 mins Spreading on cyclohexane 15 s 16s Surface tension 15.8 mN / m 15.6 mN / m Sealing on acetone (cold test) 55 mg / min 80 mg / min Sealing on acetone (fire test) 102 mg / min 113 mg / min.
  • a fluoroprotein emulsifier is prepared by proceeding as in example 1 but replacing the solution S1 with the solution Sx.
  • the fluoroprotein emulsifiers thus prepared are diluted to 3% with tap water and the resulting solutions have the characteristics indicated in the following table.
  • Example 2 3 4 5 6 7 Spreading 8.5 9.0 9.2 8.5 8.5 9.2 Spreading on cyclohexane (s) 17 13 21 21 23 48 Sealing on acetone cold test (mg / min) 54 70 70 70 59 63
  • a third of this mixture is introduced into a 500 ml reactor equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet and a device. of heating. The rest of the mixture is introduced into the dropping funnel. 0.2 g of azo-bis-isobutyronitrile is added to the reactor. A stream of nitrogen is introduced into the reactor which is maintained for the duration of the reaction. The mixture is heated to reflux at 70 ° C. with stirring. 30 minutes after the start of reflux, the contents of the dropping funnel are poured in 4 hours. 0.2 g of azo-bis-isobutyronitrile is then introduced into the reaction medium.
  • the contents of the reactor are heated to 50 ° C. 1 g of sodium and 16 g of methanol are introduced into the dropping funnel; mixing the two products leads to the formation of sodium methanolate in solution in methanol, with evolution of hydrogen.
  • the sodium methanolate solution is added dropwise to the reactor while maintaining the reactor temperature at 50 ° C.
  • the product from the hydrolysis gradually precipitates in the reaction medium.
  • the temperature is maintained at 50 ° C for 30 minutes, then cooled to room temperature.
  • the precipitate contained in the reactor is recovered by filtration on a No.
  • Example Foam concentrate Dilution rate (%) Foam application time (seconds) Power off (seconds) Re-ignition time (seconds) 90% 99% Extinction 16

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Business, Economics & Management (AREA)
  • Emergency Management (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Fire-Extinguishing Compositions (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (15)

  1. Filmbildender Fluorproteinemulgator zur Brandbekämpfung, dadurch gekennzeichnet, daß er ein Eiweißhydrolysat enthält, das verbunden ist mit:
    (a) mindestens einem fluorierten Co-Telomeren der folgenden Formel: Rf-(CH2)k-Xm-(CH2)n-Sp-(M1)q1 (M2)q2 -Y in der:
    Rf ein Perfluoralkylrest mit einer linearen oder verzweigten Kette mit mindestens 6 Kohlenstoffatomen bedeutet,
    k eine ganze Zahl von 0 bis 6 ist, die aber nicht 0 ist, wenn m 1 ist,
    X ein Sauerstoffatom oder eine COO- oder OCO-Gruppe bedeutet,
    m 0 oder 1 ist,
    n eine ganze Zahl von 0 bis 6 ist, die aber nicht 0 ist, wenn m und/oder p 1 ist,
    p 0 oder 1 ist,
    M1 eine hydrophile anionische Monomereinheit und M2 eine hydrophile nichtionische Monomereinheit bedeutet,
    q1 und q2 Zahlen sind, deren Summe zwischen 5 und 100 und das Verhältnis q2/q1 zwischen 1 und 20 liegt,
    Y ein Wasserstoffatom bedeutet, wenn p 1 ist, und ein Jod-, Brom- oder Chloratom bedeutet, wenn p 0 ist; und
    (b) mindestens einem fluorierten Tensid, von dem eine wäßrige Lösung mit 1 g/l eine Oberflächenspannung bei 20 °C von weniger als 25 mN/m besitzt.
  2. Emulgator nach Anspruch 1, in dem der Rf-Rest 6 bis 20 Kohlenstoffatome enthält, k 0 oder 2 ist, X eine OCO-Gruppe bedeutet, n 0 oder 1 ist, die Summe q1+q2 zwischen 10 und 50 liegt, Y ein Wasserstoff- oder Jodatom ist, M1 eine Einheit ist der Formel:
    Figure 00260001
    und M2 eine Einheit ist der Formel:
    Figure 00270001
    in denen die gleichen oder verschiedenen R und R' jedes ein Wasserstoffatom oder einen Methylrest bedeuten, Q1 ein Wasserstoffatom, ein Alkalimetallion oder ein quaternäres Ammoniumion und Q2 eine OH- oder CONR1R2-Gruppe bedeutet, in der jedes der gleichen oder verschiedenen Symbole R1 und R2 ein Wasserstoffatom oder einen Alkyl- oder Hydroxyalkylrest mit 1 bis 3 Kohlenstoffatomen bedeuten.
  3. Emulgator nach Anspruch 2, in dem Q1 ein Wasserstoffatom und Q2 eine OH- oder CONH2-Gruppe ist.
  4. Emulgator nach einem der Ansprüche 1 bis 3, in dem k = 0 oder 2, m = n = p = 0 und Y ein Jodatom ist.
  5. Emulgator nach einem der Ansprüche 1 bis 3, in dem k = 2, m = n = 0 oder 1, p = 1 und Y ein Wasserstoffatom ist.
  6. Emulgator nach einem der Ansprüche 1 bis 5, in dem das Verhältnis q2/q1 zwischen 1 und 10 liegt.
  7. Emulgator nach einem der Ansprüche 1 bis 6, in dem das fluorierte Tensid gewählt ist aus den Verbindungen der Formeln:
    Figure 00270002
    Figure 00270003
    Figure 00280001
    Figure 00280002
    Figure 00280003
    Rf―(CH2)w―S―(CH2)t―CONH―C(CH3)2―CH2SO3Na
    Figure 00280004
    in denen Rf ein linearer oder verzweigter Perfluoralkylrest mit mindestens 6 Kohlenstoffatomen bedeutet, s eine ganze Zahl von 0 bis 6 ist, R6 ein Wasserstoffatom oder einen Methyl- oder Ethylrest bedeutet, t und u ganze Zahlen von 1 bis 5 sind, v 2 oder 3 ist, jedes der gleichen oder verschiedenen Symbole R7, R8 und R9 einen Methyl- oder Ethylrest bedeuten und w eine ganze Zahl von 1 bis 6 ist.
  8. Emulgator nach Anspruch 7, in dem das fluorierte Tensid gewählt ist aus den Verbindungen der Formeln (VII), (VIII), (IX), (X) und (XII), wobei s = w = 2, t = v = 3, u = 1, R7 = R8 = Methyl ist und Rf 6 bis 20 Kohlenstoffatome enthält.
  9. Emulgator nach Anspruch 8, in dem das fluorierte Tensid gewählt ist aus den folgenden Verbindungen: C6F13-CH2CH2-SO2NH-CH2CH2CH2-N⊕(CH3)2-CH2-COO⊖ C6F13-CH2CH2-S-CH2-CH(OH)-CH2-N⊕(CH3)2-CH2-COO⊖ C6F13-CH2CH2-SO2NH-CH2CH2CH2-N(CH3)2→O und dem Betaingemisch der Formel: CxF2x+1-CH2CH2-SO2NH-CH2CH2CH2-N⊕(CH3)2-CH2-COO⊖ in der x eine ganze gerade Zahl von 6 bis 20 ist.
  10. Emulgator nach einem der Ansprüche 1 bis 9, der ein fluoriertes Tensid enthält, von dem eine wäßrige Lösung mit 1 g/l eine Oberflächenspannung bei 20 °C von weniger als 20 mN/m, vorzugsweise von weniger als 17 mN/m, enthält.
  11. emulgator nach einem der Ansprüche 1 bis 10, der 0,1 bis 5 Gew.-% (vorzugsweise 0,5 bis 2 Gew.-%) eines/mehrerer fluorierter Co-Telomeren und 0,5 bis 10 Gew.-% (vorzugsweise 1 bis 5 Gew.-%) eines fluorierten Tensids enthält.
  12. emulgator nach einem der Ansprüche 1 bis 11, der außerdem ein organisches mit Wasser mischbares Lösungsmittel enthält sowie ein Gefrierschutzmittel, ein Konservierungsmittel, einen pH-Stabilisator und/oder ein Korrosionsschutzmittel.
  13. Emulgator nach Anspruch 12, in dem das organische mit Wasser mischbare Lösungsmittel aus den Glykolen oder den Monoalkylethern des Mono- oder Diethylen- (oder Propylen-)glykols gewählt ist.
  14. Emulgator nach einem der Ansprüche 1 bis 13, der bei einem pH-Wert zwischen 5 und 9, vorzugsweise zwischen 6 und 8, stabilisiert ist.
  15. Verwendung eines Emulgators nach einem der Ansprüche 1 bis 14 zur Brandbekämpfung durch Kohlenwasserstoffe oder polare Flüssigkeiten.
EP96401470A 1995-07-27 1996-07-03 Polyvalenter, filmbildender Fluoroproteinemulgator Expired - Lifetime EP0755701B1 (de)

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FR9509139 1995-07-27
FR9509139A FR2737126B1 (fr) 1995-07-27 1995-07-27 Emulseurs fluoroproteiniques formant film polyvalents

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EP0755701A1 EP0755701A1 (de) 1997-01-29
EP0755701B1 true EP0755701B1 (de) 2000-03-08

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EP (1) EP0755701B1 (de)
JP (1) JPH0938235A (de)
AU (1) AU6075196A (de)
CA (1) CA2181831A1 (de)
DE (1) DE69606931T2 (de)
ES (1) ES2144707T3 (de)
FR (1) FR2737126B1 (de)

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JP5393957B2 (ja) * 2007-05-08 2014-01-22 花王株式会社 微細気泡含有液体組成物
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DE69606931D1 (de) 2000-04-13
US5824238A (en) 1998-10-20
JPH0938235A (ja) 1997-02-10
FR2737126B1 (fr) 1998-02-06
CA2181831A1 (fr) 1997-01-28
FR2737126A1 (fr) 1997-01-31
AU6075196A (en) 1997-01-30
DE69606931T2 (de) 2000-10-12
EP0755701A1 (de) 1997-01-29

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