EP0765676A1 - Fire-fighting polyvalent emulsifier - Google Patents

Abstract

Fire-resistant polyvalent emulsion comprises an aq. dispersion consisting of 0.5-10 wt.% at least one water-insoluble fluorinated copolymer prepd. from at least one fluorinated side chain monomer, at least one monomer with an ionic or ionisable hydrophilic side chain, and, eventually, one or more monomers with non-ionic side chains; 1-20 wt.% hydrocarbon surface-active agent contg. 5-18C alkyl radical (straight or branched); 0.5-10 wt.% at least one fluorinated surface-active agent with a 1 gl<-1> soln. having surface tension < 25 mNm<-1> at 20 degrees C; and 5-50 wt.% of a water-miscible organic solvent. Also claimed are: the stabilisation of the emulsion at pH at least 4 pref. 6-8; and the addition of an anti-gelling agent, an ant-corrosion agent and/or a conserving agent.

Description

The present invention relates to the extinction of fires and more particularly relates to versatile fire-fighting foam concentrates, effective both against hydrocarbon fires and against polar liquids fires. The emulsifiers according to the invention do not contain a high molecular weight thixotropic hydrophilic polymer of the polysaccharide type and are therefore perfectly fluid even at low temperature. Unlike versatile emulsifiers containing a polysaccharide, the emulsifiers according to the invention have a rheological profile of the Newtonian fluid type, that is to say that their viscosity is independent of the shear rate; this facilitates their flow in the injection and dilution systems at the time of their use.

Fire-fighting foam concentrates are an effective means of fighting fires involving combustible liquids. When in use, they are diluted in city water or sea water, 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). The quantity of active ingredients necessary to satisfy the minimum extinguishing performance required being identical in the two cases of dilution, the emulsifiers dilutable at 3% are therefore twice as concentrated as those dilutable at 6%; they allow users to store lesser amounts of foam concentrate, save space and reduce their storage costs. Recently, the demand for even more concentrated products has led manufacturers to develop 1% dilutable foam concentrates which are particularly useful in the protection of ships or oil platforms where the available space is very limited.

After diluting the foam concentrate with water, the resulting mixture produces an aqueous foam by incorporating air and supplying mechanical energy by means of a fire-fighting lance or any other foam generator. This foam is poured over fires of combustible liquids and acts by suffocation and cooling until total extinction.

To extinguish hydrocarbon fires, synthetic foam concentrates forming the AFFF (Aqueous Film Forming Foam) film have been developed; these are aqueous solutions comprising as main ingredients a mixture of fluorinated surfactants, hydrocarbon surfactants and foam stabilizing solvents, generally belonging to the glycol family. Examples of AFFF foam concentrates are described, for example, in US Patents 3,562,156, US 3,772,195, FR 2,347,426 and US 5,085,786. Fluoro-protein foam concentrates constitute the other large family of foam concentrates. In this case, the base foaming agent consists of a hydrolyzate of animal proteins to which fluorinated surfactants and foam stabilizing solvents are added. Such emulsifiers are described for example in patents GB 1,280,508 and GB 1,368,463.

The foam concentrates described above cannot be used as such for extinguishing polar liquid fires. Indeed, the foam produced from such foam concentrates is destroyed by polar liquids and cannot be used to fight such fires. Various explanations for the phenomenon of destruction of foam by polar liquids have been proposed, for example by Charovarnikov AF in "Studies on the Mechanism of Destruction of Foams by Organic Substances - Kolloidnyi Zhurnal, Vol. 42, No. 4, pp. 797-799, (1980) ", by Pletnev M.Yu. in "Mechanism of the Antifoaming Action of Polar Organic Liquids - Kolloidnyi Zhumal, Vol. 43, No. 4, pp. 826-827, (1981)" and by Dervichian DG in "Les Mousses: Formation, Stabilité, Destruction - Bulletin de the Chemical Society of France - ^5th series, pp 15-22, (1955). ".

The expression "polar liquids" is taken here in the sense accepted by those skilled in the art, that is to say to designate liquids having a certain affinity for water, the most common of which are alcohols (for example, methanol, ethanol and isopropanol), ketones (e.g. dimethyl ketone and methyl isobutyl ketone), esters (e.g. n-butyl acetate) and ethers (e.g. methyl tert-butyl ether ).

The most common method of fighting polar solvent fires is to incorporate a high molecular weight hydrophilic polymer into either of the two types of foam concentrates described above; a polysaccharide of thixotropic and alcoophobic character is generally used. A versatile foam concentrate is thus obtained, that is to say usable both on hydrocarbon fires and on polar liquid fires. When the polar liquid fires are extinguished, the polysaccharide contained in the foam precipitates on contact with the polar liquid and forms a protective gelatinous sheet which isolates the foam against the destructive action of the polar liquid. The foam can then spread over the gelatinous sheet and extinguish the fire. Such versatile emulsifiers are described in US Patents 4,464,267, US 4,149,599, FR 2,206,958 and WO 92/15371.

The extinction of polar liquid fires using a versatile foam concentrate is all the more effective when the quantity of polysaccharide present in the foam concentrate is high. On the other hand, the polysaccharides in aqueous solution being viscosifying macromolecules, they considerably increase the final viscosity of the foam concentrate, which causes pumpability problems in the injection and dilution systems, especially with cold. Under these conditions, the majority of polyvalent emulsifiers contain the necessary quantity of polysaccharide for can be diluted only to 6% on polar solvent fires. The extinguishing efficiency of these same versatile foam concentrates on hydrocarbon fires depends on ingredients other than the polysaccharide, there are versions dilutable at 3% and others dilutable at 6% on hydrocarbon fires. Multipurpose foam concentrates of the 6x6 type (6% diluted on hydrocarbon fires and 6% on polar liquid fires) and 3x6 (diluted 3% on hydrocarbon fires and 6% on polar liquid fires).

Recently, multipurpose 3x3 foam concentrates (dilutable to 3% both on hydrocarbon fires and on polar liquid fires) have been developed. The advantage of these 3x3 foam concentrates compared to 6x6 foam concentrates is that it is sufficient for an identical efficiency to store them half as much; compared to 3x6 foam concentrates, they have the advantage of being able to be used with a single mixing system whatever the type of fire and thus eliminating the risk of dosage error.

The improvement of the extinguishing efficiency on polar liquid fires and, by the same token, the development of 3x3 foam concentrates can be done in two ways.

First of all, it is possible to decrease the viscosity of the polysaccharide. Patent EP 595,772 describes the association of a polysaccharide with an anionic hydrophilic polymer making it possible to prepare low viscosity solutions, these solutions forming part of the composition of 3 × 3 polyvalent emulsifiers. Patent EP 609 827 describes the association of a polysaccharide and an alginate and indicates that the viscosity of a polyvalent 3 × 3 foam concentrate can be reduced by controlling the relative proportions of the polysaccharide and the alginate; viscosity can also be reduced by controlling the ratio of the concentration of aryl or alkylaryl sulfonic acid salts to the concentration of other hydrocarbon surfactants. However, even slightly viscous, the polysaccharide in aqueous solution leads to pseudoplastic emulsifiers whose viscosity varies with the shear rate.

According to patent ES 2 040 176, the polysaccharide is in dispersed form using hydrophobic colloidal silica and the amount of water in the foam concentrate is minimized so that the polysaccharide, which is only soluble in l water, does not increase the final viscosity of the foam concentrate. Under these conditions, the polysaccharide level can be increased until a 1x1 foam concentrate is obtained, dilutable to only 1% in water, both on hydrocarbon fires and on fires of polar liquids. In this type of foam concentrate where the amount of water must be as low as possible, the dispersing medium is a water-miscible solvent of the glycol family. Under these conditions, the need to replace the dilution water with an equivalent quantity of solvent leads to emulsifiers having a high cost price.

Another way to reduce viscosity is to decrease the level of polysaccharide in the foam concentrate. However, to maintain the same extinguishing properties of the final foam concentrate, it is necessary to increase the efficiency of the polysaccharide. The patents FR 2 636 334 and 2 637 506 describe the chemical modification of polysaccharides by grafting perfluoroalkyl groups on the hydrophilic side chains of the polysaccharide. The presence of perfluoroalkyl radicals increases the alcoophobic nature of the polysaccharide and improves its efficiency in forming an insoluble gel on the surface of the polar solvent; this makes it possible to reduce the polysaccharide content and therefore the final viscosity of the foam concentrate. However, this chemical grafting reaction requires heating at 50-70 ° C for two hours. Patent EP 524 138 relates to versatile emulsifiers 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 non-fluorinated acrylic or methacrylic monomers. In this case also, the association of the co-telomer with the polysaccharide reinforces its effectiveness and allows the incorporation of lower quantities, therefore obtaining less versatile viscous emulsifiers. Although having a reduced viscosity, these emulsifiers nevertheless retain a pseudoplastic character, the viscosity of which varies with the shear rate.

Multipurpose emulsifiers containing no polysaccharide are described in US Pat. No. 4,536,298. In this case, the polysaccharide is replaced by a cationic, water-soluble homopolymer, from the family of polyamines, polyamides and polyimines neutralized by acids. polyfunctional carboxylic; the association of the two families of products leads to a synergy which reinforces the resistance of the extinguishing foam on polar liquid.

US Patent 4,563,287 describes an extinguishing composition for cooking oil fires, containing a high molecular weight copolymer comprising perfluoroalkylated side chains and hydrophilic side chains; the hydrophilic monomer level is high enough to make the copolymer soluble in water.

Patent FR 2 438 484 describes the use of a copolymer prepared from a hydrophilic monomer and from a perfluorinated chain monomer. To be sufficiently soluble in water, the copolymer must comprise 1 to 10 hydrophilic units for each unit with a perfluorinated chain.

The present invention aims to overcome all the problems associated with the use of polysaccharides and to prepare versatile foam concentrates containing a copolymer with a high fluorine content so as to increase the performance of the foam concentrate on polar liquid fires.

However, when the level of fluorinated monomer is high, the copolymer becomes generally insoluble in water.

It has now been found that the joint use of a hydrocarbon surfactant dispersing agent and a water-miscible organic solvent makes it possible to homogeneously disperse in the aqueous phase a fluorinated copolymer insoluble in water. One can thus obtain, in the form of a stable and water-dilutable aqueous dispersion, an emulsifier comprising a fluorinated copolymer, the molar ratio of the fluorinated monomer to the hydrophilic monomer can be between 1 and 10.

• (a) de 0,5 à 10 % (de préférence 1 à 5 %) d'au moins un copolymère fluoré insoluble dans l'eau, préparé à partir d'au moins un monomère à chaîne latérale perfluorée, d'au moins un monomère à chaîne latérale hydrophile ionique ou ionisable et, éventuellement, d'un ou plusieurs monomères à chaîne latérale non-ionique ;
• (b) de 1 à 20 % (de préférence 2 à 15 %) d'au moins un agent tensio-actif hydrocarboné contenant un radical alkyle, linéaire ou ramifié, contenant de 5 à 18 atomes de carbone (de préférence 8 à 14) ;
• (c) de 0,5 à 10 % (de préférence 1 à 5 %) d'au moins un agent tensio-actif fluoré dont une solution aqueuse à 1 g/l possède une tension superficielle à 20°C inférieure à 25 mN/m, de préférence inférieure à 20 mN/m (plus particulièrement inférieure à 17 mN/m) ; et
• (d) de 5 à 50 % (de préférence 10 à 30 %) d'au moins un solvant organique miscible à l'eau.

The subject of the invention is therefore a versatile fire-fighting foam concentrate, not containing a polysaccharide, characterized in that it consists of an aqueous dispersion comprising by weight:

• (a) from 0.5 to 10% (preferably 1 to 5%) of at least one water-insoluble fluorinated copolymer, prepared from at least one monomer with a perfluorinated side chain, from at least one monomer with an ionic or ionizable hydrophilic side chain and, optionally, with one or more monomers with a nonionic side chain;
• (b) from 1 to 20% (preferably 2 to 15%) of at least one hydrocarbon-based surfactant containing an alkyl radical, linear or branched, containing from 5 to 18 carbon atoms (preferably 8 to 14) ;
• (c) from 0.5 to 10% (preferably 1 to 5%) of at least one fluorinated surfactant, an aqueous solution of 1 g / l of which has a surface tension at 20 ° C of less than 25 mN / m, preferably less than 20 mN / m (more particularly less than 17 mN / m); and
• (d) from 5 to 50% (preferably 10 to 30%) of at least one organic solvent miscible with water.

• M¹ représente une ou plusieurs unités de monomères acryliques ou méthacryliques contenant un radical perfluoroalkyle, linéaire ou ramifié, contenant 2 à 20 atomes de carbone ;
• M² représente une ou plusieurs unités de monomères acryliques, méthacryliques ou vinyliques à chaîne latérale hydrophile ionique ou ionisable ;
• M³ représente une ou plusieurs unités de monomères acryliques, méthacryliques ou vinyliques à chaîne latérale non-ionique (de préférence hydrophobe) ;
• x, y et z représentent les pourcentages massiques respectifs des unités M¹, M² et M³ réparties statistiquement dans le copolymère, x étant compris entre 50 et 95 (de préférence entre 72 et 90), y entre 1 et 25 (de préférence entre 8 et 18) et z entre 0 et 25 (de préférence entre 0 et 10), le rapport molaire de M¹ à M² étant compris entre 1 et 10, de préférence entre 1 et 3.

The fluorinated copolymer (a) can be represented by the general formula:

- [M ¹ ] _x - [M ² ] _y - [M ³ ] _z - (I)

in which

• M ¹ represents one or more units of acrylic or methacrylic monomers containing a perfluoroalkyl radical, linear or branched, containing 2 to 20 carbon atoms;
• M ² represents one or more units of acrylic, methacrylic or vinyl monomers with an ionic or ionizable hydrophilic side chain;
• M ³ represents one or more units of acrylic, methacrylic or vinyl monomers with a nonionic side chain (preferably hydrophobic);
• x, y and z represent the respective mass percentages of the units M ¹ , M ² and M ³ distributed statistically in the copolymer, x being between 50 and 95 (preferably between 72 and 90), y between 1 and 25 (preferably between 8 and 18) and z between 0 and 25 (preferably between 0 and 10), the molar ratio of M ¹ to M ² being between 1 and 10, preferably between 1 and 3.

dans laquelle R_f représente un radical perfluoroalkyle, linéaire ou ramifié, contenant 4 à 16 atomes de carbone, B représente un enchaînement bivalent lié à O par un atome de carbone et pouvant comporter un ou plusieurs atomes d'oxygène, de soufre et/ou d'azote, et R représente un atome d'hydrogène ou un radical méthyle. Ces unités M¹ proviennent d'acrylates ou méthacrylates d'alcools fluorés tels que, à titre d'exemples non limitatifs, ceux de formules :

        R_f (CH₂)_n - (X)_p - (CH₂)_m-OH     (III-a)



        R_f (CH₂)_r (OCH₂CH₂)_q-OH     (III-b)



        R_f - CH=CH - (CH₂)_m-OH     (III-c)

dans lesquelles R_f a la même signification que ci-dessus, X représente un atome d'oxygène ou de soufre ou un groupe COO, SO₂, CONR'-, -SO₂NR'-, R' représentant un atome d'hydrogène ou un radical alkyle contenant 1 à 4 atomes de carbone, n représente un nombre entier allant de 0 à 20 (de préférence égal à 0 ou 2), n n'étant pas nul si X est un atome d'oxygène ou de soufre, p est égal à 0 ou 1, les symboles m, q et r, identiques ou différents, représentent chacun un nombre entier allant de 1 à 20 (de préférence égal à 2 ou 4). On utilise préférentiellement les acrylates ou méthacrylates des alcools fluorés de formule :

        R_f - CH₂CH₂-OH     (III-d)

The units M ¹ are preferably those of formula:

in which R _f represents a linear or branched perfluoroalkyl radical containing 4 to 16 carbon atoms, B represents a bivalent chain linked to O by a carbon atom and which may contain one or more oxygen, sulfur and / or nitrogen, and R represents a hydrogen atom or a methyl radical. These units M ¹ come from acrylates or methacrylates of fluorinated alcohols such as, by way of nonlimiting examples, those of formulas:

R _f (CH ₂ ) _n - (X) _p - (CH ₂ ) _m -OH (III-a)



R _f (CH ₂ ) _r (OCH ₂ CH ₂ ) _q -OH (III-b)



R _f - CH = CH - (CH ₂ ) _m -OH (III-c)

in which R _f has the same meaning as above, X represents an oxygen or sulfur atom or a group COO, SO ₂ , CONR'-, -SO ₂ NR'-, R 'representing a hydrogen atom or an alkyl radical containing 1 to 4 carbon atoms, n represents an integer ranging from 0 to 20 (preferably equal to 0 or 2), n not being zero if X is an oxygen or sulfur atom, p is equal to 0 or 1, the symbols m, q and r, identical or different, each represent an integer ranging from 1 to 20 (preferably equal to 2 or 4). The acrylates or methacrylates of fluorinated alcohols of formula:

R _f - CH ₂ CH ₂ -OH (III-d)

dans laquelle R' représente un atome d'hydrogène ou un radical méthyle, B' représente un radical alkylène, linéaire ou ramifié, contenant 1 à 4 atomes de carbone (de préférence le radical CH₂CH₂), les symboles R¹ et R², identiques ou différents, représentent chacun un atome d'hydrogène ou un radical alkyle, linéaire ou ramifié, contenant 1 à 12 atomes de carbone (de préférence 1 à 4), hydroxyéthyle ou benzyle ou R¹ et R² ensemble avec l'atome d'azote auquel ils sont liés forment un radical morpholino, pipéridino ou pyrrolidinyle-1.The units M ² are preferably chosen from the units of acrylic or methacrylic monomers, optionally quaternized, of general formula:

in which R 'represents a hydrogen atom or a methyl radical, B' represents an alkylene radical, linear or branched, containing 1 to 4 carbon atoms (preferably the radical CH ₂ CH ₂ ), the symbols R ¹ and R ² , identical or different, each represent a hydrogen atom or an alkyl radical, linear or branched, containing 1 to 12 carbon atoms (preferably 1 to 4), hydroxyethyl or benzyl or R ¹ and R ² together with the nitrogen atom to which they are attached form a morpholino, piperidino or pyrrolidinyl-1 radical.

As nonlimiting examples of monomers leading to the M ² units of formula (IV), mention may be made of the acrylates and methacrylates of the following amino alcohols: dimethylamino-2-ethanol, diethylamino-2-ethanol, dipropylamino-2-ethanol, di -isobutylamino-2-ethanol, N-tertiobutylamino-2-ethanol, N-tertiobutyl-N-methylamino-2-ethanol, morpholino-2-ethanol, N-methyl-N-dodecylamino-2-ethanol, N-ethyl-N - (ethyl-2-hexyl) amino-2-ethanol, piperidino-2-ethanol, (pyrrolidinyl-1) -2-ethanol, diethylamino-3-propanol-1, diethylamino-2-propanol-1, dimethylamino-1- propanol-2, diethylamino-4-butanol-2.

• l'acide acrylique ou méthacrylique et leurs sels de métaux alcalins ou d'ions ammonium quaternaire ;
• l'acrylamide et ses dérivés: N-méthyl acrylamide, N-éthylacrylamide, N,N-diméthylacrylamide, N,N-diéthylacrylamide, N-méthyl-N-éthylacrylamide, N-propylacrylamide, N-isopropylacrylamide, N-(hydroxyméthyl)acrylamide, N-(3-hydroxypropyl)-acrylamide, N-(2-hydroxyéthyl)-acrylamide ;
• la N-vinylpyrrolidone-2 et ses dérivés: N-vinyl méthyl-3 pyrrolidone-2, N-vinyl méthyl-4 pyrrolidone-2, N-vinyl méthyl-5 pyrrolidone-2,
• le vinylacétamide.

As other nonlimiting examples of monomers leading to M ² units, mention may be made of:

• acrylic or methacrylic acid and their alkali metal or quaternary ammonium ion salts;
• acrylamide and its derivatives: N-methyl acrylamide, N-ethylacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-methyl-N-ethylacrylamide, N-propylacrylamide, N-isopropylacrylamide, N- (hydroxymethyl) acrylamide , N- (3-hydroxypropyl) -acrylamide, N- (2-hydroxyethyl) -acrylamide;
• N-vinylpyrrolidone-2 and its derivatives: N-vinyl methyl-3 pyrrolidone-2, N-vinyl methyl-4 pyrrolidone-2, N-vinyl methyl-5 pyrrolidone-2,
• vinylacetamide.

dans laquelle R" représente un atome d'hydrogène ou un radical méthyle, Y représente le groupement COO ou OCO ou un atome d'oxygène, et R³ désigne un groupement alkyle, hydroxyalkyle ou méthoxyalkyle contenant 1 à 18 atomes de carbone.The units M ³ which come from acrylic, methacrylic or vinyl monomers with nonionic side chain, preferably hydrophobic, are advantageously chosen from those of general formula:

in which R "represents a hydrogen atom or a methyl radical, Y represents the group COO or OCO or an oxygen atom, and R ³ denotes an alkyl, hydroxyalkyl or methoxyalkyl group containing 1 to 18 carbon atoms.

• les ester vinyliques tels que l'acétate de vinyle, le propionate de vinyle, l'isobutyrate de vinyle, l'isodécanoate de vinyle, le stéarate de vinyle;
• les éthers alkyl vinyliques, tels que le cétylvinyléther, le dodécylvinyl éther, l'isobutylvinyl éther, l'éthylvinyléther;
• les acrylates et méthacrylates d'allyle, de méthyle, d'éthyle, de butyle, d'isobutyle, d'hexyle, d'heptyle, d'éthyl-2-hexyle, de cyclohexyle, de lauryle, de stéaryle, de méthoxy-2-éthyle, d'hydroxy-2-éthyle ou d'hydroxy-2-propyle.

As nonlimiting examples of such monomers, mention may be made of:

• vinyl esters such as vinyl acetate, vinyl propionate, vinyl isobutyrate, vinyl isodecanoate, vinyl stearate;
• alkyl vinyl ethers, such as cetylvinyl ether, dodecylvinyl ether, isobutylvinyl ether, ethylvinyl ether;
• allyl, methyl, ethyl, butyl, isobutyl, hexyl, heptyl, ethyl-2-hexyl, cyclohexyl, lauryl, stearyl, methoxy acrylates and methacrylates 2-ethyl, hydroxy-2-ethyl or hydroxy-2-propyl.

The copolymer (a) can be prepared by any known method of radical copolymerization of the monomers, preferably in solution in an inert solvent or a mixture of inert solvents. The synthetic solvent can be miscible or immiscible with water. When preparing the foam concentrate, the copolymer (a) must be in solution in a water-miscible solvent. In the case where the synthesis solvent of the copolymer is immiscible with water, it should be replaced by an organic solvent miscible with water in which the copolymer (a) is soluble. The solvent for the copolymer (a) may optionally be the constituent (d).

The hydrocarbon surfactant (b) makes it possible, in combination with the solvent (d), to obtain a stable dispersion of the copolymer (a); having a foaming effect, it also makes it possible to improve the expansion of the foam concentrate.

        R_H-CONH-CH₂CH₂-NH-CH₂CH₂OCH₂CH₂COOM     (VI-d)

$${\text{R}}_{\text{H}}{\text{-N(CH}}_{\text{3}}{\text{)}}_{\text{2}}\text{→ O}$$

$${\text{R}}_{\text{H}}{\text{-N(CH}}_{\text{2}}{\text{CH}}_{\text{2}}{\text{OH)}}_{\text{2}}\text{→ O}$$

        H(C₆H₁₀O₅)_s-OR_H     (VI-j)



        R_H-(OCH₂CH₂)_t-OH     (VI-k)

        R_H-SO₃M     (VI-m)



        R_H-OSO₃M     (VI-n)

        R_H-(OCH₂CH₂)_t'-OSO₃M     (VI-q)

        R_H-COOM     (VI-s)



        R_H-CON(CH₃)CH₂COOM     (VI-t)

dans lesquelles R_H désigne un radical alkyle, linéaire ou ramifié, contenant de 5 à 18 atomes de carbone (de préférence 8 à 14), M représente un équivalent d'ion métallique alcalin, alcalino-terreux ou ammonium quaternaire, s est un nombre entier allant de 1 à 6 (de préférence égal à 1 ou 2), t un nombre entier allant de 6 à 20 (de préférence 8 à 16), t' un nombre entier allant de 1 à 6 (de préférence de 2 à 4).The hydrocarbon-based surfactants which can be used in the emulsifier may be of anionic, cationic, nonionic or amphoteric nature. Non-limiting examples that may be mentioned include the compounds of the following formulas:

R _H -CONH-CH ₂ CH ₂ -NH-CH ₂ CH ₂ OCH ₂ CH ₂ COOM (VI-d)

$${\text{R}}_{\text{H}}{\text{-N (CH}}_{\text{3}}{\text{)}}_{\text{2}}\text{→ O}$$

$${\text{R}}_{\text{H}}{\text{-N (CH}}_{\text{2}}{\text{CH}}_{\text{2}}{\text{OH)}}_{\text{2}}\text{→ O}$$

H (C ₆ H ₁₀ O ₅ ) _s -OR _H (VI-j)



R _H - (OCH ₂ CH ₂ ) _t -OH (VI-k)

R _H -SO ₃ M (VI-m)



R _H -OSO ₃ M (VI-n)

R _H - (OCH ₂ CH ₂ ) _{t '} -OSO ₃ M (VI-q)

R _H -COOM (VI-s)



R _H -CON (CH ₃ ) CH ₂ COOM (VI-t)

in which R _H denotes an alkyl radical, linear or branched, containing from 5 to 18 carbon atoms (preferably 8 to 14), M represents an equivalent of alkali metal ion, alkaline earth metal or quaternary ammonium, s is a number integer ranging from 1 to 6 (preferably equal to 1 or 2), t an integer ranging from 6 to 20 (preferably 8 to 16), t 'an integer ranging from 1 to 6 (preferably 2 to 4 ).

        R_F - (CH₂)_u' - S - (CH₂)_v - CONH - C(CH₃)₂ -CH₂SO₃Na     (VII-g)

dans lesquelles R_F représente un radical perfluoroalkyle, linéaire ou ramifié, contenant au moins 6 atomes de carbone, u est un nombre entier allant de 0 à 6, R⁴ représente un atome d'hydrogène ou un radical méthyle ou éthyle, v et w sont des nombres entiers allant de 1 à 5, w' est égal à 2 ou 3, les symboles R⁵, R⁶ et R⁷, identiques ou différents, représentent chacun un radical méthyle ou éthyle, et u' est un nombre entier allant de 1 à 6.The fluorinated surfactant (s) to be used according to the invention can be chosen, without limitation, from the compounds of formulas:

R _F - (CH ₂ ) _{u '} - S - (CH ₂ ) _v - CONH - C (CH ₃ ) ₂ -CH ₂ SO ₃ Na (VII-g)

in which R _F represents a linear or branched perfluoroalkyl radical containing at least 6 carbon atoms, u is an integer ranging from 0 to 6, R ⁴ represents a hydrogen atom or a methyl or ethyl radical, v and w are whole numbers ranging from 1 to 5, w 'is equal to 2 or 3, the symbols R ⁵ , R ⁶ and R ⁷ , identical or different, each represent a methyl or ethyl radical, and u' is an integer ranging from 1 to 6.

$${\text{C}}_{\text{6}}{\text{F}}_{\text{13}}{\text{- CH}}_{\text{2}}{\text{CH}}_{\text{2}}{\text{- SO}}_{\text{2}}{\text{NH - CH}}_{\text{2}}{\text{CH}}_{\text{2}}{\text{CH}}_{\text{2}}{\text{- N(CH}}_{\text{3}}{\text{)}}_{\text{2}}{\text{→ O C}}_{\text{6}}{\text{F}}_{\text{13}}{\text{- CH}}_{\text{2}}{\text{CH}}_{\text{2}}{\text{- SO}}_{\text{2}}{\text{N(CH}}_{\text{3}}{\text{) - CH}}_{\text{2}}{\text{CH}}_{\text{2}}{\text{CH}}_{\text{2}}{\text{-N(CH}}_{\text{3}}{\text{)}}_{\text{2}}\text{→ O}$$

ainsi que les mélanges de bétaïnes de formule:

les mélanges de sulfobétaïnes de formule :

les mélanges d'oxydes d'amines de formule : $${\text{C}}_{\text{k}}{\text{F}}_{\text{2k+1}}{\text{- CH}}_{\text{2}}{\text{CH}}_{\text{2}}{\text{- SO}}_{\text{2}}{\text{NH - CH}}_{\text{2}}{\text{CH}}_{\text{2}}{\text{CH}}_{\text{2}}{\text{- N(CH}}_{\text{3}}{\text{)}}_{\text{2}}\text{→ O}$$

formules dans lesquelles k est un nombre entier pair allant de 6 à 16, la teneur du mélange en composé à radical C₆F₁₃ étant d'au moins 50 % en poids.As examples of fluorinated surfactants (c), the following compounds may be mentioned more particularly:

$${\text{VS}}_{\text{6}}{\text{F}}_{\text{13}}{\text{- CH}}_{\text{2}}{\text{CH}}_{\text{2}}{\text{- N / A}}_{\text{2}}{\text{NH - CH}}_{\text{2}}{\text{CH}}_{\text{2}}{\text{CH}}_{\text{2}}{\text{- N (CH}}_{\text{3}}{\text{)}}_{\text{2}}{\text{→ OC}}_{\text{6}}{\text{F}}_{\text{13}}{\text{- CH}}_{\text{2}}{\text{CH}}_{\text{2}}{\text{- N / A}}_{\text{2}}{\text{N (CH}}_{\text{3}}{\text{) - CH}}_{\text{2}}{\text{CH}}_{\text{2}}{\text{CH}}_{\text{2}}{\text{-N (CH}}_{\text{3}}{\text{)}}_{\text{2}}\text{→ O}$$

as well as the betaine mixtures of formula:

mixtures of sulfobetaines of formula:

mixtures of amine oxides of formula: $${\text{VS}}_{\text{k}}{\text{F}}_{\text{2k + 1}}{\text{- CH}}_{\text{2}}{\text{CH}}_{\text{2}}{\text{- N / A}}_{\text{2}}{\text{NH - CH}}_{\text{2}}{\text{CH}}_{\text{2}}{\text{CH}}_{\text{2}}{\text{- N (CH}}_{\text{3}}{\text{)}}_{\text{2}}\text{→ O}$$

formulas in which k is an even whole number ranging from 6 to 16, the content of the mixture of compound with radical C ₆ F ₁₃ being at least 50% by weight.

The water-miscible organic solvent (d) must be inert and a good solvent for the copolymer (a). It can be a single solvent miscible with water or a mixture of several solvents; in this case, the mixture must be generally miscible with water, even if it contains one or more solvents immiscible with water. As nonlimiting examples, mention may be made of monoalkyl ethers of mono- or di-ethylene (or propylene) glycol, ketones such as acetone, methyl ethyl ketone or methyl isobutyl ketone, alcohols such as methanol, ethanol, isopropanol or tertiobutanol, N-methylpyrrolidone, γ-butyrolactone, DMSO. Certain glycol ethers, such as n-butyl diglycol, or the tert-butyl ether of propylene glycol, also have good foam stabilizing power and they increase the expansion of the foam concentrate. It is therefore recommended to use them in admixture with the solvents described above. It is the same for the well-known antifreeze power of ethylene glycol, the latter solvent can then be used in combination with one or more other solvents.

• un agent antigel comme l'éthylène glycol ou le propylène glycol,
• un agent anticorrosion tel que le tolyltriazole ou le nitrite de sodium,
• un agent conservateur tel que le benzoate de sodium, le formaldéhyde, l'o-phénylphénol ou le dichlorophène,
• un stabilisateur de pH tel que l'ammoniaque, la diéthanolamine, la triéthanolamine.

In addition to components (a), (b), (c) and (d), the foam concentrate can also contain various additives such as:

• an antifreeze agent such as ethylene glycol or propylene glycol,
• an anticorrosion agent such as tolyltriazole or sodium nitrite,
• a preservative such as sodium benzoate, formaldehyde, o-phenylphenol or dichlorophene,
• a pH stabilizer such as ammonia, diethanolamine, triethanolamine.

In order to obtain optimum performance, the foam concentrate according to the invention is advantageously stabilized at a pH at least equal to 4, preferably between 6 and 8.

The preparation of the foam concentrate is carried out by simple mixing of the constituents (a), (b), (c), (d) and others optionally at room temperature or by heating to a moderate temperature and with stirring. The foam concentrate is then diluted with tap water or sea water at a rate of 0.5 to 6 parts by volume, preferably 1 to 3 parts by volume per 100 parts by volume in total. The resulting extinguishing composition is used to fight fires of hydrocarbons and polar liquids.

The performance of the foam concentrates according to the invention can be evaluated by means of the following tests:

Spreading

The overrun (or expansion rate) is the ratio of the volume of foam produced from a 3% aqueous solution of foam concentrate to the volume of initial liquid. To determine the overrun, 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 circular piston perforated (30 holes of 5 mm in diameter representing 25% of the surface) and fixed in its center to a metal rod.

Hydrocarbon spreading test

This test which indicates the speed of formation of the aqueous film on the surface of the hydrocarbons is carried out 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. When the surface of the hydrocarbon is stationary, 0.5 ml of a 3% aqueous solution of emulsifier is deposited using a micro pipette. 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.

Foam tightness test on polar liquid

There is an automatic balance connected to a recorder. Poured into a crystallizer 9.8 cm in diameter placed on the scale pan 50 ml of polar solvent (acetone). On the other hand, the foam concentrate is diluted to 3% in tap water and the foam is produced using an electric mixer for 2 minutes. About 18 g of foam are deposited on the polar solvent. The balance is reset to zero and the weight loss due to evaporation of the polar liquid is noted as a function of time. The results are expressed in mg / min.

The most efficient foam concentrates to give a foam which is impermeable 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 fires. In this case, the procedure is identical but the polar liquid is ignited and allowed to burn for 90 seconds before pouring the foam to extinguish it. The amount of polar liquid used is 150 ml and about 50 g of foam are poured.

The acetone evaporation rate should be less than 85 mg / min for the cold test and less than 150 mg / min for the fire test.

EXAMPLES

In the following examples which illustrate the invention without limiting it, the percentages indicated are expressed by weight and the main constituents used are designated, for simplicity, by the following abbreviations:

   commercialisé en solution aqueuse à 30 % sous la dénomination Deriphat 160C par la société HENKEL.
B ₃ = alkyl (C₈ et C₁₀)-amidoétherpropionate de formule :

        Alkyl - CONH - CH₂CH₂ - NH - CH₂CH₂OCH₂CH₂COONa

   commercialisé en solution aqueuse à 50% sous la dénomination Rewoteric AMVSF par la société REWO.
B ₄ = alkyl (C₈ et C₁₀)-glucoside commercialisé en solution aqueuse à 60 % sous la dénomination Triton CG-110 par la société UNION CARBIDE.
B ₅ = alkyl (C₁₂ et C₁₄) N-hydroxyéthylimidazoline de formule :

   commercialisé en solution aqueuse à 40 % sous la dénomination Sochamine A7527 par la société WITCO.
B ₆ = octyl sulfate de sodium commercialisé en solution aqueuse à 42 % sous la dénomination Texapon 842 par la société HENKEL.
B ₇ = lauryl éther sulfate de formule :

        C₁₂H₂₅ - (OCH₂CH₂)₂ - OSO₃Na

   commercialisé en solution aqueuse à 30% sous la dénomination Neopon LOS par la société WITCO.
B ₈ = lauroyl sarcosinate de sodium commercialisé en solution aqueuse à 30 % sous la référence GM 9011 par la société ZSCHIMMER & SCHWARTZ.
B ₉ = alkyl (radical coprah) oxyde d'amine de formule : $${\text{Alkyl - N (CH}}_{\text{2}}{\text{CH}}_{\text{2}}{\text{OH)}}_{\text{2}}\text{→ O}$$

   commercialisé en solution aqueuse à 30 % sous la dénomination Noxamine C2-30 par la société CECA.
B ₁₀ = sel d'alkyl (radical coprah) ammonium quaternaire de formule :

        alkyl - N^⊕(CH₃)₃ Cl^⊖

   commercialisé en solution aqueuse à 50 % sous la dénomination Noramium MC 50 par la société CECA
B ₁₁ = sel d'alkyl (radical coprah) ammonium quaternaire de formule :

        Alkyl - N^⊕(CH₃)(CH₂CH₂OH)₂Cl^⊖

   commercialisé en solution aqueuse à 50 % sous la dénomination Noxamium MS 2-50 par la société CECA
B ₁₂ = lauryl diméthyl amine oxyde : $${\text{C}}_{\text{12}}{\text{H}}_{\text{25}}{\text{-N(CH}}_{\text{3}}{\text{)}}_{\text{2}}\text{→ O}$$

   commercialisé en solution aqueuse à 30 % sous la dénomination Rewominox L408 par la Société REWO.
C ₁ = oxyde d'amine fluorée de formule : $${\text{C}}_{\text{6}}{\text{F}}_{\text{13}}{\text{- CH}}_{\text{2}}{\text{CH}}_{\text{2}}{\text{- SO}}_{\text{2}}{\text{NH - CH}}_{\text{2}}{\text{CH}}_{\text{2}}{\text{CH}}_{\text{2}}{\text{- N(CH}}_{\text{3}}{\text{)}}_{\text{2}}\text{→ O}$$

   commercialisé par la Demanderesse sous forme de solution hydroalcoolique à 40 %.
C ₂ = bétaïne fluorée de formule :

        C₆F₁₃ - CH₂CH₂ - SO₂NH - CH₂CH₂CH₂ - ^⊕N(CH₃)₂CH₂COO^-

   commercialisée par la Demanderesse sous forme de solution hydroalcoolique à 27 %.
C ₃ = mélange de bétaïnes fluorées de formule :

        C_nF_2n+1 - CH₂CH₂ - SO₂NH - CH₂CH₂CH₂ - ^⊕N(CH₃)₂CH₂COO^⊖

ayant la composition pondérale suivante : M _1a = mixture of fluorinated acrylates of formula:

CH ₂ = CH - COO - C ₂ H ₄ - (CF ₂ ) _n CF ₃

having the following weight composition: not % 5 1 7 63 9 25 11 9 13 2
M _1b = mixture of fluorinated acrylates of formula:

CH ₂ = CH - COO - C ₂ H ₄ - N (CH ₃ ) - SO ₂ - C ₂ H ₄ - (CF ₂ ) _n CF ₃

having the following weight composition: not % 5 57 7 30 9 9 11 3 13 1
M _2a = N, N-dimethylaminoethyl methacrylate:

CH ₂ = C (CH ₃ ) - COO - C ₂ H ₄ - N (CH ₃ ) ₂


M _2b = N-tert-butylaminoethyl methacrylate:

CH ₂ = C (CH ₃ ) - COO - C ₂ H ₄ - NH - C (CH ₃ ) ₃


M _3a = ethylene glycol methacrylate:

CH ₂ = C (CH ₃ ) - COO - C ₂ H ₄ - OH


M _3b = vinyl acetate:

CH ₂ = CH - OCO - CH ₃


B ₁ = (C ₁₂ and C ₁₄ ) -amidopropylbetaine alkyl 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 Amphotensid B4 by the company ZSCHIMMER & SCHWARTZ.
B ₂ = N-lauryl-β-iminodipropionate of formula:

sold in 30% aqueous solution under the name Deriphat 160C by the company HENKEL.
B ₃ = (C ₈ and C ₁₀ ) alkylamidoetherpropionate of formula:

Alkyl - CONH - CH ₂ CH ₂ - NH - CH ₂ CH ₂ OCH ₂ CH ₂ COONa

marketed in 50% aqueous solution under the name Rewoteric AMVSF by the company REWO.
B ₄ = (C ₈ and C ₁₀ ) alkyl glucoside sold in a 60% aqueous solution under the name Triton CG-110 by the company UNION CARBIDE.
B ₅ = (C ₁₂ and C ₁₄ ) N-hydroxyethylimidazoline alkyl of formula:

sold in 40% aqueous solution under the name Sochamine A7527 by the company WITCO.
B ₆ = sodium octyl sulfate sold in 42% aqueous solution under the name Texapon 842 by the company HENKEL.
B ₇ = lauryl ether sulfate of formula:

C ₁₂ H ₂₅ - (OCH ₂ CH ₂ ) ₂ - OSO ₃ Na

sold in 30% aqueous solution under the name Neopon LOS by the company WITCO.
B ₈ = sodium lauroyl sarcosinate sold in a 30% aqueous solution under the reference GM 9011 by the company ZSCHIMMER & SCHWARTZ.
B ₉ = alkyl (copra radical) amine oxide of formula: $${\text{Alkyl - N (CH}}_{\text{2}}{\text{CH}}_{\text{2}}{\text{OH)}}_{\text{2}}\text{→ O}$$

marketed in 30% aqueous solution under the name Noxamine C2-30 by the company CECA.
B ₁₀ = alkyl salt (copra radical) quaternary ammonium of formula:

alkyl - N ^⊕ (CH ₃ ) ₃ Cl ^⊖

sold in 50% aqueous solution under the name Noramium MC 50 by the company CECA
B ₁₁ = alkyl salt (copra radical) quaternary ammonium of formula:

Alkyl - N ^⊕ (CH ₃ ) (CH ₂ CH ₂ OH) ₂ Cl ^⊖

sold in 50% aqueous solution under the name Noxamium MS 2-50 by the company CECA
B ₁₂ = lauryl dimethyl amine oxide: $${\text{VS}}_{\text{12}}{\text{H}}_{\text{25}}{\text{-N (CH}}_{\text{3}}{\text{)}}_{\text{2}}\text{→ O}$$

marketed in a 30% aqueous solution under the name Rewominox L408 by the company REWO.
C ₁ = fluorinated amine oxide of formula: $${\text{VS}}_{\text{6}}{\text{F}}_{\text{13}}{\text{- CH}}_{\text{2}}{\text{CH}}_{\text{2}}{\text{- N / A}}_{\text{2}}{\text{NH - CH}}_{\text{2}}{\text{CH}}_{\text{2}}{\text{CH}}_{\text{2}}{\text{- N (CH}}_{\text{3}}{\text{)}}_{\text{2}}\text{→ O}$$

marketed by the Applicant in the form of a 40% hydroalcoholic solution.
C ₂ = fluorinated betaine of formula:

C ₆ F ₁₃ - CH ₂ CH ₂ - SO ₂ NH - CH ₂ CH ₂ CH ₂ - ^⊕ N (CH ₃ ) ₂ CH ₂ COO ^-

marketed by the Applicant in the form of a 27% hydroalcoholic solution.
C ₃ = mixture of fluorinated betaines of formula:

C _n F _{2n + 1} - CH ₂ CH ₂ - SO ₂ NH - CH ₂ CH ₂ CH ₂ - ^⊕ N (CH ₃ ) ₂ CH ₂ COO ^⊖

having the following weight composition:

not % 6 70 8 23 10 5 12 1.5 14 0.4 16 0.1 marketed by the Applicant in the form of a 27% hydroalcoholic solution.

EXAMPLE 1

P ₁ denotes a fluorinated copolymer obtained by radical polymerization of a mixture of monomers having the following composition: monomers contents% M _1a 85 M _2a 15

a) Synthesis of the copolymer P ₁

90 g are loaded into a 500 ml reactor equipped with an agitator, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet and a heating device. of N-methylpyrrolidone, 20 g of acetone, 15 g of monomer M _2a , 0.8 g of 4,4'-azobis (cyano-4-pentanoic acid) and 85 g of monomer M _1a . The mixture is heated to 85 ° C. under a nitrogen atmosphere for 6 hours, then 8 g of acetic acid in 150 g of water are added. It is kept for another hour at 75 ° C., then cooled to room temperature. The copolymer P _{1 is} thus obtained in solution with 27.9% of dry extract.

b) Preparation of an foam concentrate

The appropriate quantities of copolymer P1 and the other constituents are mixed at ambient temperature and with moderate stirring, then the mixture is adjusted to pH 7 by addition of diethanolamine. An emulsifier according to the invention is thus obtained, the contents of active materials of which are as follows: constituents contents% P ₁ 2.4 B ₁ 4.5 C ₂ 1.4 ethanol 1.7 butyl diglycol 15 acetone 0.5 N-methyl pyrrolidone 2.3 water (qs 100%) 72.2

• Indice de réfraction (20°C) : 1,369
• Viscosité (20°C - 10,8 s^-1) : 8,8mPa.s
• Tension superficielle (3 % eau de ville) : 18,6mN/m
• Tension interfaciale (3 % eau de ville/cyclohexane) : 3,5 mN/m
• Coefficient d'étalement sur cyclohexane : + 3,2 mN/m

This versatile fire-fighting foam concentrate has the following characteristics:

• Refractive index (20 ° C): 1.369
• Viscosity (20 ° C - 10.8 s ^-1 ): 8.8 mPa.s
• Surface tension (3% city water): 18.6mN / m
• Interface tension (3% city water / cyclohexane): 3.5 mN / m
• Spreading coefficient on cyclohexane: + 3.2 mN / m

• Foisonnement : 7,5
• Etalement sur cyclohexane : 38 secondes
• Test d'étanchéité à l'acétone - test à froid : 42mg/min
• Test d'étanchéité à l'acétone - test sur feu : 86mg/min

Subjected to the tests described above, this foam concentrate leads to the following performances:

• Spread: 7.5
• Spreading on cyclohexane: 38 seconds
• Acetone tightness test - cold test: 42mg / min
• Acetone tightness test - fire test: 86 mg / min

EXAMPLE 2

P ₂ denotes a fluorinated copolymer obtained by radical polymerization of a mixture of monomers having the following composition: monomers contents% M _1a 76 M _2a 15 M _3b 9

a) Synthesis of the copolymer P ₂

The procedure is as for the synthesis of P ₁ , but after the addition of the 15 g of monomer M _2a , 9 g of monomer M _{3b are added} and then 76 g of monomer M _1a . The copolymer P _{2 is} thus obtained in solution with 27.9% of dry extract.

b) Preparation of an foam concentrate

The appropriate quantities of copolymer P ₂ and the other constituents are mixed at ambient temperature and with moderate stirring, then the mixture is adjusted to pH 7 by addition of diethanolamine. An emulsifier according to the invention is obtained, the contents of active materials of which are as follows:

constituents contents% P ₂ 2.5 B ₄ 6 C ₂ 1.4 ethanol 1.7 butyl diglycol 15 acetone 0.6 N-methyl pyrrolidone 2.7 water (qs 100%) 70.1

• Indice de réfraction (20°C) : 1,370
• Viscosité (20°C - 10,8 s^-1) : 7,4mPa.s
• Tension superficielle (3 % eau de ville) : 18,3mN/m
• Tension interfaciale (3 % eau de ville/cyclohexane) : 1,2 mN/m
• Coefficient d'étalement sur cyclohexane : + 5,8 mN/m

This versatile fire-fighting foam concentrate has the following characteristics:

• Refractive index (20 ° C): 1,370
• Viscosity (20 ° C - 10.8 s ^-1 ): 7.4mPa.s
• Surface tension (3% city water): 18.3mN / m
• Interface tension (3% city water / cyclohexane): 1.2 mN / m
• Spread coefficient on cyclohexane: + 5.8 mN / m

• Foisonnement: 5
• Etalement sur cyclohexane : 8 secondes
• Etalement sur mélange cyclohexane/n-heptane (75 %/25 %) : 12 s
• Etalement sur mélange cyclohexane/n-heptane (50 %/50 %) : 19 s
• Test d'étanchéité à l'acétone - test à froid : 31 mg/min
• Test d'étanchéité à l'acétone - test sur feu : 61 mg/min

Subjected to the tests described above, this foam concentrate leads to the following performances:

• Spread: 5
• Spreading on cyclohexane: 8 seconds
• Spread on cyclohexane / n-heptane mixture (75% / 25%): 12 s
• Spread on cyclohexane / n-heptane mixture (50% / 50%): 19 s
• Acetone tightness test - cold test: 31 mg / min
• Acetone tightness test - fire test: 61 mg / min

EXAMPLES 3 TO 23

By proceeding as in Example 2-a, other fluorinated copolymers according to the invention P ₃ to P ₆ were synthesized, the composition of which is summarized in the following table: COPOLYMER Monomers Content (%) P ₃ M _1b / M _2a / M _3b 76/15/9 P ₄ M _1a / M _2a / M _3a 84/10/6 P ₅ M _1a / M _2a / M _3b 81/14/5 P ₆ M _1a / M _2b / M _3b 76/15/9

By operating as in Examples 1b and 2b, a series of versatile fire-fighting foam concentrates was prepared, the constituents of which (nature and content in the foam concentrate) are shown in the following table; the contents of the ingredients are expressed as a percentage by mass of active ingredients. The foam concentrates are completed up to 100% by addition of water.

Subjected to the tests described above, these foam concentrates lead to the following performances: Example foam concentrate: Cyclohexane spreading test Leak test with acetone (mg / min) Cold test Fire test 3 60% 51 98 4 9s 40 76 5 11s 33 71 6 7s 61 101 7 10 s 64 95 8 9s 67 91 9 8s 61 107 10 58s 31 89 11 65% 70 97 12 12s 56 141 13 95% 53 90 14 8s 58 89 15 9s 54 86 16 4s 46 108 17 6s 47 80 18 8s 40 79 19 7s 42 82 20 12s 38 69 21 6s 37 72 22 25s 36 66 23 25s 37 66

EXAMPLES 24 AND 25 (COMPARATIVE)

An emulsifier is prepared by proceeding as in Example 3 but the copolymer P ₂ is removed which does not replace an equivalent amount of water (Example 24).

On the other hand, the procedure is as in Example 1-b but the fluorinated surfactant C ₂ is removed, which is replaced by an equivalent amount of water (Example 25).

Subjected to the tests described above, these foam concentrates lead to the following performances:

Example foam concentrate: Cyclohexane spreading test Leak test with acetone (mg / min) Cold test Fire test 24 11s 125 385 25 not filming 47 95

The absence of fluorinated copolymer in the foam concentrate of Example 24 does not make it possible to obtain a stable foam on polar solvent; it disappears immediately and the acetone evaporation rate is very high. The absence of fluorinated surfactant in the foam concentrate of Example 25 does not make it possible to obtain the formation of the aqueous film on cyclohexane. These two foam concentrates are not versatile.

EXAMPLES 26 to 29

A series of extinction tests is carried out according to standard NF S 60225 - Reference test on an acetone source of 0.25 m ² . The dilution rate is 3% in city water. The results of the extinction tests are reported in the following table: Example Foam concentrate Foam application time (seconds) Power off (seconds) Re-ignition time (seconds) 90% 99% Extinction 26 Example 5 foam concentrate 240 120 125 140 330 27 Example 22 foam concentrate 240 80 120 135 800 28 Example 23 foam concentrate 120 45 65 110 440 29 comparison Example 24 foam concentrate 240 No extinction -

Claims (14)

Versatile fire-fighting foam concentrate characterized in that it consists of an aqueous dispersion comprising by weight: (a) from 0.5 to 10% of at least one fluorinated copolymer insoluble in water, prepared from at least one monomer with a perfluorinated side chain, from at least one monomer with an ionic or ionizable hydrophilic side chain and, optionally, one or more monomers with a nonionic side chain; (b) from 1 to 20% of at least one hydrocarbon-based surfactant containing an alkyl radical, linear or branched, containing from 5 to 18 carbon atoms; (c) from 0.5 to 10% of at least one fluorinated surfactant, an aqueous solution of 1 g / l of which has a surface tension at 20 ° C of less than 25 mN / m; and (d) from 5 to 50% of at least one organic solvent miscible with water. An emulsifier according to claim 1 in which the fluorinated copolymer corresponds to the general formula:

- [M ¹ ] _x - [M ² ] _y - [M ³ ] _z - (I)

in which M ¹ represents one or more units of acrylic or methacrylic monomers containing a perfluoroalkyl radical, linear or branched, containing 2 to 20 carbon atoms; M ² represents one or more units of acrylic, methacrylic or vinyl monomers with an ionic or ionizable hydrophilic side chain; M ³ represents one or more units of acrylic, methacrylic or vinyl monomers with a nonionic side chain (preferably hydrophobic); x, y and z represent the respective mass percentages of the units M ¹ , M ² and M ³ distributed statistically in the copolymer, x being between 50 and 95, y between 1 and 25 and z between 0 and 25, the molar ratio of M ¹ to M ² being between 1 and 10. An emulsifier according to claim 2 in which x is between 72 and 90, y between 8 and 18 and z between 0 and 10, the molar ratio of M ¹ to M ² being between 1 and 3. Foam concentrate according to claim 2 or 3 in which the units M ¹ are chosen from those of general formula:

in which R _f represents a linear or branched perfluoroalkyl radical containing 4 to 16 carbon atoms, B represents a bivalent chain linked to O by a carbon atom and which may contain one or more oxygen, sulfur and / or nitrogen, and R represents a hydrogen atom or a methyl radical. Emulsifier according to one of claims 2 to 4 in which the units M ² are chosen from units of acrylic or methacrylic monomers, optionally quaternized, of general formula:

in which R 'represents a hydrogen atom or a methyl radical, B' represents an alkylene radical, linear or branched, containing 1 to 4 carbon atoms, the symbols R ¹ and R ² , identical or different, each represent an atom hydrogen or a linear or branched alkyl radical containing 1 to 12 carbon atoms (preferably 1 to 4), hydroxyethyl or benzyl or R ¹ and R ² together with the nitrogen atom to which they are attached form a radical morpholino, piperidino or pyrrolidinyl-1. An emulsifier according to claim 4 or 5 in which B and / or B 'is a CH ₂ CH ₂ radical. Foam concentrate according to one of Claims 2 to 6, in which the units M ³ are chosen from those of general formula:

in which R '' represents a hydrogen atom or a methyl radical, Y represents the COO or OCO group or an oxygen atom, and R ³ denotes an alkyl, hydroxyalkyl or methoxyalkyl group containing 1 to 18 carbon atoms. Emulsifier according to one of claims 1 to 7 in which the hydrocarbon-based surfactant (s) are chosen from the compounds of formula:

R _H -CONH-CH ₂ CH ₂ -NH-CH ₂ CH ₂ OCH ₂ CH ₂ COOM (VI-d)

$${\text{R}}_{\text{H}}{\text{-N (CH}}_{\text{3}}{\text{)}}_{\text{2}}\text{→ O}$$

$${\text{R}}_{\text{H}}{\text{-N (CH}}_{\text{2}}{\text{CH}}_{\text{2}}{\text{OH)}}_{\text{2}}\text{→ O}$$

H (C ₆ H ₁₀ O ₅ ) _s -OR _H (VI-j)



R _H - (OCH ₂ CH ₂ ) _t -OH (VI-k)

R _H -SO ₃ M (VI-m)



R _H -OSO ₃ M (VI-n)

R _H - (OCH ₂ CH ₂ ) _{t '} -OSO ₃ M (VI-q)

R _H -COOM (VI-s)



R _H -CON (CH ₃ ) CH ₂ COOM (VI-t)

in which R _H denotes an alkyl radical, linear or branched, containing from 5 to 18 carbon atoms (preferably 8 to 14), M represents an equivalent of alkali metal ion, alkaline earth metal or quaternary ammonium, s is a number integer ranging from 1 to 6 (preferably equal to 1 or 2), t an integer ranging from 6 to 20 (preferably 8 to 16) and t 'an integer ranging from 1 to 6 (preferably 2 to 4) . Emulsifier according to one of Claims 1 to 8, in which the fluorinated surfactant (s) are chosen from the compounds of formula:

R _F - (CH ₂ ) _{u '} - S - (CH ₂ ) _v - CONH - C (CH ₃ ) ₂ -CH ₂ SO ₃ Na (Vll-g)

in which R _F represents a linear or branched perfluoroalkyl radical containing at least 6 carbon atoms, u is an integer ranging from 0 to 6, R ⁴ represents a hydrogen atom or a methyl or ethyl radical, v and w are whole numbers ranging from 1 to 5, w 'is equal to 2 or 3, the symbols R ⁵ , R ⁶ and R ⁷ , identical or different, each represent a methyl or ethyl radical, and u' is an integer ranging from 1 to 6. Emulsifier according to one of claims 1 to 9 containing a fluorinated surfactant, an aqueous solution of 1 g / l of which has a surface tension at 20 ° C of less than 20 mN / m, preferably less than 17 mN / m. Foam concentrate according to one of Claims 1 to 10, characterized in that it contains by weight 1 to 5% of copolymer (a), 2 to 15% of hydrocarbon-based surfactant (b), 1 to 5% of fluorinated surfactant (c) and 10 to 30% organic solvent (d). Foam concentrate according to one of claims 1 to 11 stabilized at a pH at least equal to 4, preferably between 6 and 8. Foam agent according to one of claims 1 to 12, further comprising an antifreeze agent, an anti-corrosion agent and / or a preservative. Use of an foam concentrate according to one of claims 1 to 13 for combating hydrocarbon fires or polar solvent fires.