FR2748662A1 - VERSATILE ANTI-FIRE EMULSE - Google Patents

Abstract

The invention features fire-extinguishing emulsifiers for hydrocarbon and polar liquid fires. These polyvalent emulsifiers, without polysaccharide, comprise: (a) at least one telomer containing fluorine having a perfluoroalkyl radical and a polymerized chain consisting of units of at least one hydrophilic monomer, and (b) at least one hydrophilic polymer not containing fluorine obtained by radical polymerization of hydrophilic monomers.

Description

DESCRIPTION
The present invention relates to extinguishing fires and more particularly to multipurpose fire extinguishing emulsifiers, that is to say, effective against both hydrocarbon fires and fires of polar liquids. The emulsifiers according to the invention do not contain a polysaccharide and are therefore perfectly fluid even at low temperature. In contrast to polyvalent emulsifiers containing a polysaccharide, the emulsifiers according to the invention are weakly viscous and have a rheological profile of the Newtonian fluid type, ie their viscosity is independent of the shear rate; this facilitates their flow into the injection and dilution systems at the time of their use.

The emulsifiers according to the invention which may be synthetic or proteinic, are characterized in that they comprise:
(a) at least one fluorinated telomer having a perfluoroalkyl radical and a polymerized chain consisting of hydrophilic monomer units, and
(b) at least one non-fluorinated hydrophilic polymer obtained by radical polymerization of hydrophilic monomers.

 The use of fluorinated surfactants in hydrocarbon fire fighting emulsifiers is well known, both in the case of synthetic emulsifiers and in that of protein emulsifiers. The quenching performance of these fluorinated emulsifiers is greater than that of the non-fluorinated emulsifiers.

At the time of use, the emulsifiers are diluted in tap water or sea water, usually at a volume concentration of 3% (ie 3 volumes of foam concentrate for 97 volumes of water ) or 6% (6 volumes of foam concentrate for 94 volumes of water). Since the amount of active material required to satisfy the minimum required fire-fighting performance is identical in both cases of dilution, the 3% dilutable foamers are thus twice as concentrated as those dilutable at 6%; they allow users to store smaller amounts of foam concentrate, save space and reduce storage costs. Recently, the demand for even more concentrated products has led manufacturers to develop 1% dilutable foam concentrates that are particularly useful in the protection of ships or oil rigs where space is very limited.

 The mixture resulting from the dilution of the emulsifier produces an aqueous foam by incorporation of air and supply of mechanical energy by means of a fire extinguisher. This foam is poured on the fires of combustible liquids and acts by choking and cooling until total extinction.

For extinguishing hydrocarbon fires, US Patents 3,562,156,
US 3,772,195, FR 2,347,426 and US 5,085,786 describe the preparation and use of AFFF (Aqueous Film Forming Foam) film forming emulsifiers which consist of aqueous solutions comprising, as main ingredients, a mixture of fluorinated surfactants, hydrocarbon surfactants and water-miscible organic solvents, foam stabilizers, generally belonging to the families of glycols and glycol ethers. The patents GB 1 280 508 and GB 1 368 463 describe fluoroprotein emulsifiers whose foaming base consists of a hydrolyzate of animal proteins to which are added fluorinated surfactants and foam stabilizing solvents.

 The emulsifiers described above can not be used for extinguishing fires of polar liquids, the term "polar liquids" being taken here in the sense accepted by those skilled in the art, that is to say to designate the liquids with a certain affinity for water, the most common of which are alcohols (for example methanol, ethanol and isopropanol), ketones (for example dimethylketone and methyl isobutyl ketone), esters (for example n-butyl acetate) and ethers (for example methyl tertiary butyl ether).

To extinguish this type of hearth, a polysaccharide of thixotropic and alcoholic character is generally incorporated in the emulsifier; it is generally an anionic heteropolysaccharide bearing carboxylic groups neutralized with sodium, potassium or calcium cations or a quaternary ammonium ion. Commercial products are generally in the form of powders dilutable in water with strong agitation. This gives a versatile emulsifier, that is to say, used on both hydrocarbon fires and fires of polar liquids. The preparation and use of such polysaccharide-containing emulsifiers as an alcohophobic agent are described in US Pat. Nos. 4,149,599 and 4,464,267.
FR 2 206 958 and WO 9215371. During extinction, the polysaccharide contained in the foam precipitates in contact with the polar liquid and forms a protective gelatin sheet which isolates the foam against the destructive action of the polar liquid. The foam can then spread over the gelatinous layer and extinguish the fire.

 The extinction of the polar liquid fires with a polyvalent emulsifier is all the more effective that the amount of polysaccharide present in the emulsifier is important. But in return, the polysaccharides in aqueous solution being viscosifying macromolecules, they significantly increase the final viscosity of the emulsifier, which causes pumpability problems in the injection and dilution systems, especially with the cold. Under these conditions, most polyvalent emulsifiers contain the necessary amount of polysaccharide to be diluted only to 6% on polar solvent fires. The extinguishing efficiency of these same hydrocarbon fuels based on ingredients other than the polysaccharide, there are versions dilutable to 3% and other dilutable 6% on hydrocarbon fires. We then obtain 6x6 type multi-purpose emulsifiers (dilutable at 6% on hydrocarbon fires and 6% on polar liquid fires) and 3x6 (dilutable at 3% on hydrocarbon fires and at 6% on fires). fires of polar liquids).

 Recently, 3x3 multipurpose emulsifiers (3% dilutable on both hydrocarbon fires and polar liquid fires) have been developed.

The advantage of these 3x3 emulsifiers compared to 6x6 emulsifiers is that it is sufficient for an identical efficiency to store two times less. Compared to 3x6 emulsifiers, they have the advantage of being able to be used with one and the same mixing system whatever the type of fire and thus to eliminate the risk of dosing error.

To achieve this goal, several ways to reduce the viscosity of polysaccharide-based polyvalent emulsifiers have been proposed in the US Pat.
FR 2,636,334, 2,637,506, EP 524,138, EP 595,772 and EP 609,827. In all cases, although having a reduced viscosity, the described emulsifiers still retain a pseudoplastic character whose viscosity varies with shear rate and temperature, which can cause problems when dosing at the time of use. In addition, protein-based emulsifiers often contain iron in the form of ferrous chloride or sulphate, which poses compatibility problems with polysaccharides bearing anionic carboxylate groups and causes some deposition. Finally, when the polysaccharide-containing emulsifiers are stored in steel tanks, for example in high-capacity fixed protective systems, slight oxidation occurs on the tank walls or in the metal pipes which releases iron ions. and causes in the long term, as described above, a certain deposit which may hinder the evacuation of the emulsifier.

 ES 2,040,176 discloses the preparation of a multipurpose emulsifier wherein the polysaccharide is in dispersed form using hydrophobic colloidal silica and the amount of water in the emulsifier is minimized so that the polysaccharide which is soluble only in water, does not increase the final viscosity of the emulsifier. However, since the polysaccharide is not solubilized but dispersed, this emulsifier is not a homogeneous solution but a heterogeneous dispersion sensitive to phase separation problems during storage or during sedimentation determination tests in which the The emulsifier is subjected by centrifugation to high accelerations. For example, during the centrifugation test of the French standard NF S 60-210 (paragraph 7.1) the sample is subjected to an acceleration of 6000m / s-2 i 1000m / s-2 for 10 minutes.

The emulsifiers according to the invention are perfectly clear and homogeneous aqueous solutions which have no deposit or phase shift when they are centrifuged.

Non-polysaccharide-containing polyvalent emulsifiers are described in US Pat. No. 4,536,298. In this case, the polysaccharide is replaced by a water-soluble cationic homopolymer of the family of polyamines, polyamines or polyimines neutralized with polyfunctional carboxylic acids. ;
The combination of the two families of products leads to a synergy which reinforces the resistance of the foam extinguishing on polar liquid. However, the use of entirely cationic homopolymers does not make it possible to have a composition that is perfectly compatible with all the fluorinated surfactants or anionic hydrocarbon surfactants commonly used in emulsifiers. The mixtures of the present invention are predominantly nonionic and therefore universally applicable irrespective of the ionic nature of the surfactants of the emulsifiers in which they are used.

 US Pat. No. 4,563,287 discloses fire-fighting emulsifiers containing a high molecular weight copolymer having perfluoroalkyl side chains and hydrophilic side chains. However, in contrast to the present invention, this patent claims only effective emulsifiers on hydrocarbon fires and more specifically on cooking oil fires but not on polar liquids.

 Patent FR 2 438 484 describes the use of a copolymer prepared from a hydrophilic monomer and a monomer bearing a perfluoroalkyl chain.

However, for the polymer to be globally soluble in water, it is composed of one or more hydrophilic units for each perfluoroalkyl chain unit so that the amount of fluorine that can be incorporated is limited. However, the perfluoroalkylated groups have an alcoholic character that is beneficial for the resistance of the foam to polar liquids. The efficiency is therefore limited to satisfy the overall solubility of the polymer.

 The object of the present invention is to obtain polyvalent synthetic or proteinaceous emulsifiers which do not contain polysaccharides, these polyvalent emulsifiers being dilutable with water at a level of between 1 and 6% on hydrocarbon and between 1 and 6% also on liquid. polar. The invention is aimed in particular at the preparation of polyvalent emulsifiers of the 6x6, 3x6, 3x3 and even lxi type, and the transformation of an effective commercial emulsifier solely on hydrocarbon fires into a polyvalent emulsifier effective on hydrocarbon fires and fires. polar liquids.

 It has now been found that the joint addition of a telomer carrying a perfluoroalkyl radical and a hydrophilic nonfluorinated polymer makes it possible to make polyvalent, that is to say used both on hydrocarbon fires and on polar liquid fires, an ineffective synthetic or proteinic emulsifier on polar liquid fires. According to the invention, a telomer carrying a perfluoroalkyl radical and a hydrophilic nonfluorinated polymer are incorporated in the synthetic or proteinic fire-fighting emulsifiers to enhance their resistance to polar liquids.

 The synthetic fire-fighting foamers contain as foaming base one or more non-fluorinated anionic, nonionic or amphoteric surfactants. In the case of AFFF emulsifiers, these additionally contain one or more fluorogenic surfactants with a film-forming nature capable of greatly reducing the surface tension; anionic, cationic or amphoteric fluorinated surfactants are generally used.

The protein fire-fighting foam concentrates contain as foaming base a hydrolyzate of animal proteins obtained by basic attack of residues of horns, hairs, hooves or hemoglobin from cattle, followed by neutralization with an acid. As in the case of synthetic emulsifiers, the addition of one or more fluorinated film-forming surfactants makes it possible to prepare fluoroprotein film forming emulsifiers called FFFP emulsifiers (Forming Film).
Fluoroprotein).

The subject of the invention is therefore a polyvalent fire-fighting emulsifier containing no polysaccharide, characterized in that it comprises, by weight, per 100 parts by weight of emulsifier:
(a) from 0.5 to 15 parts (preferably from 1 to 10 parts, and more preferably from 2 to 8 parts) of at least one fluorinated telomer having a perfluoroalkyl radical and a polymerized chain consisting of hydrophilic monomer units , and
(b) from 0.03 to 10 parts (preferably from 0.1 to 6 parts, and more particularly from 0.5 to 4 parts) of at least one non-fluorinated hydrophilic polymer obtained by radical polymerization of one or more hydrophilic monomers.

 The polymerized chain of the fluorinated telomer (a) preferably consists of units of a nonionic hydrophilic monomer and optionally an anionic hydrophilic monomer. The non-fluorinated hydrophilic polymer (b) is preferably obtained from at least one nonionic hydrophilic monomer and optionally from at least one cationic hydrophilic monomer.

The fluorinated telomeres may be chosen from compounds of formula:
Rf - (CH2) k - Xm - (CH2) n - Sp - (M1) q1 (M2) q2 - Y (I) in which:
Rf represents a linear or branched chain perfluoroalkyl radical containing at least 6 carbon atoms, preferably 6 to 20 carbon atoms,
k is an integer ranging from 0 to 6, but different from O if m is equal to 1,
X represents an oxygen atom or a CO 2 or OCO group,
m is 0 or 1,
n is an integer ranging from 0 to 6, but different from O if m and / or p is equal to 1,
pestaltoOou 1,
M1 represents an anionic hydrophilic monomer unit and M2 a nonionic hydrophilic monomer unit,
q1 and q2 are numbers whose sum is between 5 and 100, the ratio q1 / q2 being between 0 and 2, preferably between 0 and 1,
Y represents a hydrogen atom when p is equal to 1 and an iodine, bromine or chlorine atom when p is 0.

As examples of anionic hydrophilic monomer leading to the unit
M1, mention may be made without limitation:
acrylic acid, methacrylic acid and their alkali metal salts or quaternary ammonium ions;
the monoolefinic derivatives of sulphonic acid and their alkali metal salts, such as, for example, sodium ethylenesulphonate, sodium styrenesulphonate and 2-acrylamido-2-methylpropanesulphonic acid.

As examples of nonionic hydrophilic monomer leading to the unit M2. we can mention without limitation:
Acrylamide, methacrylamide and their derivatives such as N-methyl-acrylamide, N-ethyl-acrylamide, N, N-dimethyl-acrylamide, N-methyl-N-ethyl-acrylamide, N-hydroxymethyl acrylamide, N- (2-hydroxyethyl) -acrylamide, N- (3hydoxypropyl) -acrylamide;
N-vinyl derivatives, such as N-vinylacetamide, N-vinylpyrrolidone-2, N-vinylmethyl-3-pyrrolidone-2, N-vinylmethylpyrrolidone-2, Nvinylmethylpyrrolidone, 2;
acrylates or methacrylates of aminoalcohols such as, for example, N, Ndimethylamino-2-ethanol, N, N-diethylamino-2-ethanol, N-ethyl-N-methylamino-2-ethanol, pyrrolidinyl-1) -2-ethanol, methylamino-1-propanol-2;
Vinyl acetate, followed by telomerization by hydrolysis to obtain units of polyvinyl alcohol.

les unités de monomère hydrophile non-ionique M2 correspondent préférentiellement à la formule générale:

dans lesquelles R1 et R2, identiques ou différents, représentent chacun un atome d'hydrogène ou un radical méthyle, Q1 représente un atome d'hydrogène, un ion métallique alcalin ou un ion ammonium quaternaire, et Q2 représente un groupe OH ou un groupe CONR3R4 dans lequel les symboles R3 et R4, identiques ou différents, représentent chacun un atome d'hydrogène ou un radical alkyle ou hydroxyalkyle contenant de 1 à 3 atomes de carbone.Among the fluorinated telomeres of formula (I), those in which k is equal to O or 2, X represents the group OCO, n is equal to 0 or 1, the sum q1 + q2 is between 10 and 50, Y is preferred. is a hydrogen or iodine atom, the anionic hydrophilic monomer M1 units preferably correspond to the general formula:

the nonionic hydrophilic monomer units M2 preferably correspond to the general formula:

in which R1 and R2, which may be identical or different, each represent a hydrogen atom or a methyl radical, Q1 represents a hydrogen atom, an alkaline metal ion or a quaternary ammonium ion, and Q2 represents an OH group or a CONR3R4 group in which the symbols R3 and R4, which are identical or different, each represent a hydrogen atom or an alkyl or hydroxyalkyl radical containing from 1 to 3 carbon atoms.

 Among the compounds mentioned above for the choice of the monomer leading to M1 units, acrylic acid, methacrylic acid and their alkali metal salts are preferred. For the choice of the monomer leading to the M2 units, acrylamide or methacrylamide is preferred.

When in the fluorinated telomeres of formula (I), the ratio q1 / q2 is different from 0, the distribution of the units M1 and M2 may be statistical. The formula (I) is therefore only a schematic representation of the telomeres and does not claim to describe the exact arrangement of the M1 and M2 units in the molecule. The fluorinated telomers of formula (I) may be prepared in a manner known per se by reacting a fluorinated telogen agent of general formula:
Wherein Rf, k, X, m, n, p, and Y have the same meaning as above, with (s) hydrophilic (s) in the presence of a radical initiator. We can operate in different ways, for example:
by mixing all the reagents (initiator, telogen, monomers);
by flowing simultaneously on the fluorinated telogen contained in the reactor, on the one hand the mixture of the monomers and, on the other hand, a solution of the radical initiator;
by simultaneously flowing on the one hand the fluorinated telogen containing the initiator and on the other hand the mixture of the monomers
It is desirable to operate in solution in a solvent chosen from alcohols (preferably methanol, ethanol, isopropanol or tert-butanol) and glycol ethers, in particular glymes (preferably mono and diglyme). ).

 The radical initiator may be an azo initiator such as, for example, azobisisobutyronitrile or 4, 4'-azo-bis-cyanopentanoic acid, or peroxide 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 may vary from 0.5 to 25% by weight relative to the telogen depending on the relative reactivity of the telogen and the monomers. The reaction temperature is 0 to 150 ° C, preferably 60 to 90 ° C.

 The preparation of the telomeres can also be carried out in two stages, for example comprising a step of telomerizing a single nonionic hydrophilic monomer, followed by partial hydrolysis transforming a fraction of the nonionic hydrophilic units into anionic hydrophilic units. Thus, for example, it is possible to partially hydrolyze the acrylamide derivatives or the aminoalcohol acrylates to acrylic acid; the telomer resulting from the hydrolysis then has both types of units in the polymerized hydrophilic part.

As telogenic agents of formula (IV) of particular interest in the context of the present invention, the following may be mentioned, Rf having the same meaning as in formula (I):
perfluoroalkyl iodides: Rf - I
leading to the telomeres (I) in which k = m = n = p = 0;
2- (perfluoroalkyl) ethyl iodides: Rf - CH 2 CH 2 - I
leading to the telomeres (I) in which k = 2 and m = n = p = 0;
2- (perfluoroalkyl) ethyl mercaptans: Rf-CH 2 CH 2 -SH
leading to the telomeres (I) in which k = 2, m = n = 0 and p = 1;
- thioglycolates of fluorinated alcohols: Rf - CH2CH2 - OCO - CH2 SH
leading to the telomeres (I) in which k = 2 and m = n = p = 1.

 The non-fluorinated hydrophilic polymers that can be used in the context of the invention are synthetic polymers obtained by radical polymerization of hydrophilic monomers, preferably at least one nonionic hydrophilic monomer and optionally at least one cationic hydrophilic monomer. The cationic hydrophilic monomer makes it possible to increase the interaction between the hydrophilic polymer (b) and the fluorinated telomer (a) in the case where the latter has at least one anionic monomer in its polymerized chain. However, it is possible to have a hydrophilic polymer (b) containing at least one cationic hydrophilic monomer even if the fluorinated telomer (a) does not have anionic hydrophilic monomer in its polymerized chain. Similarly, the fluorinated telomer (a) may contain one or more anionic monomers even if the hydrophilic polymer (b) does not contain a cationic hydrophilic monomer.

 The hydrophilic polymer (b) according to the invention is prepared by radical polymerization in a manner known per se.

 It is possible to carry out the polymerization in aqueous solution. In this case the monomers are soluble in the medium, as well as the polymer (b). At the end of the polymerization, the polymer may be stored in the form of an aqueous solution used as it is, or it may be isolated in the form of a powder containing 100% of active ingredients by precipitation in a water-miscible liquid but wherein the polymer is insoluble, followed by washing and filtration. Among the liquids capable of precipitating the polymer include, for example, lower alcohols such as methanol, ethanol and isopropanol and ketones such as dimethyl ketone, methyl ethyl ketone and methyl isobutyl ketone. The polymerization reaction may be initiated by a water-soluble initiator such as, for example, the persulfate ion (S2082-) which decomposes under the action of heat and produces a radical which initiates the polymerization reaction or by a redox couple such as, for example, the mixture persulfate (S2082 -) / metabisulphite (S2052-) whose oxidation-reduction reaction produces a radical which initiates the polymerization reaction. The use of a redox couple makes it possible to polymerize at a lower temperature than in the case of an initiator used alone. The polymerization can be carried out in the presence of various other ingredients such as a transfer agent that allows to regulate the molecular weight or a buffer mixture that avoids too large variations in pH.

The polymerization can also be carried out in a precipitating medium in a solvent capable of solubilizing both the monomers and the initiator but not the polymer that precipitates during its formation. A short hydrocarbon-chain solvent is preferably used, for example acetonitrile or methanol.
Ethanol, isopropanol. The solvent may consist of a mixture of one of the abovementioned solvents and water, but in this case the proportion of water must be less than 10% by weight of the mixture so that the polymer which is hydrophilic is generally insoluble in the solvent. Since the polymer is soluble in water, the addition of limited amounts of water in the solvent has the effect of slightly increasing the solubility of the polymer and retarding its precipitation; this makes it possible to obtain higher molecular weights. Thus, it is possible to vary the molecular weight of the polymer by adjusting the amount of water.

 The reaction can take place in batch or casting. At the end of the polymerization, the polymer is recovered in powder form with 100% active ingredients.

As a polymerization initiator, 4,4'-azo-bis- (4-cyanopentanoic acid) or azobis-isobutyronitrile may be chosen without limitation.

- les acrylates et les méthacrylates d'aminoalcools répondant à la formule:

dans lesquelles R5 et R6, identiques ou différents, représentent chacun un atome d'hydrogène ou un radical méthyle, R8 et R9, identiques ou différents, représentent chacun un atome d'hydrogène, un radical alkyle ou un radical hydroxyalkyle contenant de 1 à 3 atomes de carbone, R10 et R1 identiques ou différents, représentent chacun un radical alkyle ou hydroxyalkyle contenant 1 à 4 atomes de carbone, B représente un radical alkylène ou hydroxyalkylène contenant de 1 à 4 atomes de carbone;
- I'acétate de vinyle, la polymérisation étant suivie d'une hydrolyse qui transforme le polyacétate de vinyle hydrophobe résultant en alcool polyvinylique hydrophile.As nonlimiting examples of nonionic hydrophilic monomers usable for the preparation of the hydrophilic nonfluorinated polymer (b), mention may be made of those already mentioned for the selection of nonionic hydrophilic monomers leading to the M2 units of the fluorinated telomer (a). Among these, we preferentially choose:
Acrylamide, methacrylamide and their derivatives corresponding to the formula:

acrylates and methacrylates of aminoalcohols corresponding to the formula:

in which R5 and R6, which are identical or different, each represent a hydrogen atom or a methyl radical, R8 and R9, which may be identical or different, each represent a hydrogen atom, an alkyl radical or a hydroxyalkyl radical containing from 1 to 3 carbon atoms, R10 and R1, which may be identical or different, each represent an alkyl or hydroxyalkyl radical containing 1 to 4 carbon atoms, B represents an alkylene or hydroxyalkylene radical containing from 1 to 4 carbon atoms;
Vinyl acetate, the polymerization being followed by hydrolysis which converts the resulting hydrophobic vinyl polyacetate into hydrophilic polyvinyl alcohol.

dans laquelle R7 représente un atome d'hydrogène ou un radical méthyle, R12, R13 et R14, identiques ou différents, représentent chacun un radical alkyle ou hydroxyal kyle contenant 1 à 4 atomes de carbone, B' représente un radical alkylène ou hydroxyalkylène contenant de 1 à 4 atomes de carbone, A- est un anion monovalent quelconque.As cationic hydrophilic monomers possibly used for the preparation of the polymer (b), preference is given to:
acrylates and methacrylates of aminoalcohols corresponding to the formula:

in which R7 represents a hydrogen atom or a methyl radical, R12, R13 and R14, which may be identical or different, each represent an alkyl or hydroxyalkyl radical containing 1 to 4 carbon atoms, B 'represents an alkylene or hydroxyalkylene radical containing 1-4 carbon atoms, A- is any monovalent anion.

 Nonionic hydrophilic monomers of particular interest in the context of the invention are chosen from acrylamide, methacrylamide, N, N-dimethylamino-2-ethanol acrylate and N, N-dimethylamino-ethanol methacrylate. .

 In order to avoid any interaction problem with the fluorinated or anionic hydrocarbon surfactants that may be present in the emulsifiers, the nonionic hydrophilic monomer (or monomers) predominate in the polymer (b) relative to the cationic hydrophilic monomer (or monomers). . This makes it possible to obtain emulsifiers according to the invention which are clear and homogeneous; for this, the hydrophilic polymer (b) contains from 80 to 100%, preferably from 93 to 100%, in moles of at least one hydrophilic nonionic monomer and from 0 to 20%, preferably from 0 to 7% in moles of at least one cationic hydrophilic monomer.

 During the preparation of the hydrophilic polymer (b), it is possible to incorporate one or more crosslinking agents which have the effect of creating bonds between the hydrophilic chains; a hydrophilic polymer (b) is then obtained which is more or less crosslinked as a function of the concentration of crosslinking agent. As crosslinking agents, mention may be made, without limitation, of compounds having at least two polymerizable double bonds, such as divinyl ketone, N, N-methylene-bisacrylamide, N, N-methylene-bis-methacrylamide and glyoxal. bis-acrylamide, bis-acrylamido-acetic acid, allyl methacrylate and ethylene glycol dimethacrylate. The amount of crosslinking agent that can be incorporated in the polymer (b) is between 0 and 0.5% (preferably between 0 and 0.1%) by weight relative to the hydrophilic monomers.

 Incorporation into the emulsifier of components (a) and (b) does not require special conditions of temperature or pH. Constituents (a) and (b) may be incorporated for example at room temperature with moderate agitation at any stage of the preparation of the emulsifiers. The two components (a) and (b) can be premixed as a ready-to-use solution and incorporated all at once in the emulsifier. This last point is interesting for the ease of implementation because one can thus transform an effective commercial synthetic or proteinic emulsifier on hydrocarbon fires but inefficient on fires (a) and 0.1 to 20%, preferably 1 to 10%, of at least one nonfluorinated hydrophilic polymer (b).

 In addition to the constituents (a) and (b), a synthetic emulsifier of the 3x3 type according to the invention comprises, by weight, from 1 to 10% (preferably from 2 to 5%) of at least one hydrocarbon surfactant, from 5 to 30% (preferably from 10 to 20%) of at least one water-miscible organic solvent, generally a glycol or a glycol ether and more particularly a mono- or diethylene monoalkyl ether (or propylene glycol.

 For the preparation of a synthetic emulsifier AFFF, is added to a synthetic emulsifier as described above from 0.5 to 5% (preferably from 1 to 3%) of at least one film-forming fluorosurfactant , that is to say a fluorinated surfactant of which a 1 g / l aqueous solution has a surface tension at 20 ° C of less than 20 mN / m, preferably less than 17 mN / m.

 For the preparation of a protein type 3x3 emulsifier according to the invention, a protein hydrolyzate is used, the solids content of which is usually about 20 to 50% by weight and to which, in addition, constituents are added ( a) and (b), from 5 to 30% (preferably from 10 to 20%) of at least one water-miscible organic solvent, generally a glycol or a glycol ether and more particularly a monoalkyl ether of mono or diethylene (or propylene) glycol.

 To a protein emulsifier as described above, from 0.5 to 5% (preferably from 1 to 3%) of at least one fluorinated film-forming surfactant can be added to obtain a fluoroproteinic film-forming emulsifier. FFFP.

The synthetic or proteinaceous fire-fighting emulsifiers may optionally contain various other additives such as an antifreeze agent (for example ethylene glycol or propylene glycol), a co-solvent (for example a lower alcohol in C1 to
C4), an anticorrosion agent, a preservative, a pH stabilizer, mineral salts whose cation is divalent, such as, for example, the magnesium ion or the calcium ion; as an example of such salts, there may be mentioned calcium chloride, magnesium chloride and magnesium sulfate.

The multipurpose fire-fighting foamers according to the invention are used to combat hydrocarbon fires and polar liquids. Their performance can be evaluated using the following tests:
expansion
The expansion (or expansion ratio) is the ratio of the volume of foam produced from a 3% aqueous solution of emulsifier to the initial volume of liquid.

To determine the expansion, 100 ml of aqueous 3% emulsifier solution are introduced into a 1-liter test tube, and the solution is then beaten for one minute at a rate of one beat per second using a circular piston. perforated (30 holes 5 mm in diameter representing 25% of the surface) and fixed at its center to a metal rod. The volume in milliliters of foam obtained is measured and, dividing by 100, the value of the expansion is obtained.

Hydrocarbon spreading test
This test, which indicates the rate 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 (inner diameter: 11.8 cm) whose outer face is painted black so to be able to watch the movie When the surface of the hydrocarbon is immobile, 0.5 ml of a 3% aqueous solution of emulsifier is deposited using a micropipette.

The solution should be dripped from the center and eccentric. The stopwatch is triggered when the first drop is deposited and stopped when the film has covered the entire surface of the hydrocarbon. We note the time in seconds. If the total recovery is not obtained in less than one minute, the percentage of surface covered after one minute is noted.

Stability of the foam on polar liquid
100 ml of acetone are poured into a crystallizer 11.8 cm inside diameter.

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. 10 + 2 g of foam is poured on the acetone and triggers the stopwatch. The total disappearance time of the foam is noted. The best performing emulsifiers on polar liquid are those for which the time of total disappearance of the foam is the longest possible. For the polyvalent emulsifiers according to the invention, the time of total disappearance of the foam must be greater than 90 seconds.

Fire extinguishing effectiveness on polar fluid
150 ml of acetone are poured into a circular metal container 12 cm inside diameter. On the other hand, an aqueous solution consisting of the emulsifier diluted to 3% in tap water is prepared. There is a rotary agitator consisting of a motor and a metal rod at the end of which are fixed blades that produce a mechanical action when the rod is rotating; the rotation speed is adjustable from 0 to 2800 rpm. The stem is introduced into the bottom of a cylindrical container. The cylindrical container has an inlet at the bottom and an outlet at the top. A metering pump transfers the aqueous solution through the inlet to the bottom of the cylindrical container; in contact with the rotating blades, foam occurs which is evacuated, as and when it is formed, through the outlet orifice. The flow rate of the pump and the speed of rotation of the rod are adjusted so that foam is produced continuously with a fixed foam rate of between 30 and 40 g / min. Under these conditions, dividing by the surface of the metal container containing acetone, we obtain an application rate of between 2.65 and 3.54 g / min.m2.

 When the foam flow rate is stabilized, the acetone is ignited. After burning acetone for 90 seconds, the foam is poured into the metal container through a single point on the circumference. When acetone is completely extinguished, the extinction time and the foam flow rate are noted.

The amount of foam spilled to extinguish the fire is calculated by multiplying the time by the flow. The best performing emulsifiers on polar liquid are those for which the quantity of foam spilled is the lowest possible. For multipurpose foamers according to the invention, the amount of foam poured must be less than 85 g.

EXAMPLES
In the following examples which illustrate the invention, without limiting it, the quantities are expressed in parts by weight, except in particular cases mentioned specified.

The symbols Rf1, Rf2, Rf3, Rf4 and Rf5 each represent a mixture of linear perfluoroalkyl radicals. The relative proportions of the various perfluoroalkyl radicals in mass% in the mixtures designated Rf1, Rf2, Rf3, Rf4, Rf5 are indicated in the following table.

<Tb>

<SEP> Rf1 <SEP> Rf2 <SEP> Rf3 <SEP> Rf4 <SEP> Rf5
<tb> C6F13 <SEP> 49.0 <SEP> 0.4 <SEP> 0 <SEP> 0 <SEP> 70.0
<tb> C8F17 <SEP> 36.2 <SEP> 64.3 <SEP> 64.1 <SEP> 4.1 <SEP> 23.0
<tb> C10F21 <SEP> 12.0 <SEP> 26.8 <SEP> 27.4 <SEP> 75.3 <SEP> 5.0
<tb> C12F25 <SEP> 2.8 <SEP> 6.5 <SEP> 7.0 <SEP> 15.1 <SEP> 1.5
<tb> C14F29 <SEP> 0 <SEP> 1.5 <SEP> 1.5 <SEP> 5.1 <SEP> 0.4
<tb> C16F33 <SEP> 0 <SEP> 0.5 <SEP> 0 <SEP> 0.4 <SEP> 0.1
<Tb>
The key constituents of the invention, namely fluorinated telomeres on the one hand and non-fluorinated hydrophilic polymers on the other hand are designated, for simplicity, respectively by the abbreviations A1 to A7 and B1 to B18.

A1 = 30% aqueous solution of the fluorinated telomer of formula:
Rf2 [CH2-CH (CONH2)] 17 - [CH2-CH (COOH)] 3 - I prepared according to the following procedure:
In a one liter reactor equipped with a heating device, a stirrer, a thermometer, a nitrogen inlet and a reflux condenser, 55 g of tert-butanol, 1 g of azo-bis-isobutyronitrile and 58.5 g (0.1 mole) of perfluoroalkyl iodide Rf2 - I. By maintaining a stream of nitrogen, the temperature is increased to 80 C in 30 minutes. Then, the following two solutions are run simultaneously in 3 h 30 min: solution Si: - 120.7 g (1.7 moles) of acrylamide
- 21.6 g (0.3 mole) of acrylic acid
330 g of tert-butanol solution S2: 10 g of azobis-isobutyronitrile
- 50 g of N-methyl pyrrolidone
The telomere precipitates after a few minutes. At the end of the introduction of the two solutions S1 and S2, it is still maintained at 80 C for 2 hours. 280 g of tert-butanol are then distilled off, then 550 g of water are added and 211 g of the water-tert-butanol azeotrope are distilled off. A solution (Al) at 30% solids content of the fluorinated telomer of formula above is thus obtained.

A2 = 30% aqueous solution of the fluorinated telomer of formula:
Rf2 [CH2-CH (CONH2)] 16 - [CH2-CH (COOH)] 4 - I prepared as above, but using a solution S1 composed of 113.6 g (1.6 moles) of acrylamide, 28, 8 g (0.4 mole) acrylic acid and 330 g tert-butanol.

A3 = 20% aqueous solution of the fluorinated telomer of formula: Rf4 @ [CH2-CH (CONH2)] 20 - I prepared by operating as follows:
In a 1-liter reactor equipped with a heating device, a stirrer, a thermometer, a nitrogen inlet and a reflux condenser, 98 g of tert-butanol, 1.8 g of g of azo-bis-isobutyronitrile and 119 g (0.18 moles) of perfluoroalkyl iodide R * - I. By maintaining a stream of nitrogen, the temperature is increased to 85 C in 30 minutes. Then, the following two solutions are run simultaneously in 3 h 30 min: solution S1: - 256 g (3.6 moles) of acrylamide
- 594 g of tertiobutanol solution S2: -18 g of azobis-isobutyronitrile
90 g of N-methyl-pyrrolidone
At the end of the introduction of the two solutions S1 and S2, still maintained at 85 C for 2 hours. 449 g of tert-butanol are then distilled, and then 500 g of water are added. The solution obtained is evaporated in an oven and then water is added until 2026 g of a solution (A3) at 20% solids content of the fluorinated telomer of formula above is obtained.

A4 = 20% aqueous fluorinated telomer solution of formula: Rf4 - [CH2-CH (CONH2)] 16 - [CH2-CH (COOH)] 4 - I prepared from solution A3 according to the following procedure:
112.5 g of the solution A3 obtained above are mixed with a solution of 1.6 g of sodium hydroxide in 4 g of water, and the mixture is then heated at 70 ° C. for 2 hours. The infra-red analysis of the resulting product reveals a characteristic band of the COO- carboxylate group at 1565 cm -1. It is adjusted with water to obtain the solution (A4) at 20% solids.

As = 20% aqueous solution of the fluorinated telomer of formula:
Rf1 - C2H4 - OCO - CH2 - S - [CH2 - CH (CONH2)] 16 - [CH2 - CH (COOH) 4 --H prepared by operating as follows:
In a one-liter reactor equipped with a heating device, a stirrer, a thermometer, a nitrogen inlet and a reflux condenser, 55 g of tert-butanol and 0.03 g are introduced. 4.4'-azo-bis-cyanopentanoic acid. By maintaining a current of nitrogen, the temperature is increased to 80 ° C. in 30 minutes.

Then, the following two solutions are run simultaneously in 3 h 30 min: solution S1: - 50 g of tertiobutanol
- 1 g of 4,4'-azo-bis-cyanopentanoic acid
51.6 g (0.1 mol) of 2 - (perfluoroalkyl) ethanol thioglycolates of
mule: Rf1 - C2H4 OCOCH2SH good solution S2 - 113.6 g (1.6 moles) of acrylamide
- 28.8 g (0.4 mole) of acrylic acid
330 g of tertiobutanol
30 minutes after the start of the casting solutions S1 and S2, 0.5 g of 4,4'-azo-bis-cyanopentanoic acid is added. At the end of the introduction of the two solutions S1 and S2, 0.2 g of 4,4'-azo-bis-cyanopentanoic acid is added and the temperature is maintained at 80 ° C. for 2 hours. 256 g of tert-butanol are then distilled off, then 500 g of water are added and 202 g of the azeotropic eaultertiobutanol distilled off. 724 g of a 26% solids solution are obtained which is adjusted by addition of water to obtain a 20% solution (A5) of the fluorinated telomer of formula above.

A6 = 22% aqueous solution of the fluorinated telomer formula:
C6F13 - C2H4 - S - [CH2-CH (CONH2)] 16 - [CH2-CH (COOH)] 4 - H prepared according to the following procedure:
In the same apparatus as above, 55 g of tert-butanol and 0.03 g of 4,4'-azo-bis-cyanopentanoic acid are introduced. By maintaining a current of nitrogen, the temperature is increased to 80 ° C. in 30 minutes. Then, the following two solutions are run simultaneously over the course of 3 h 30 min: Si solution: 38 g (0.1 mol) of 2- (perfluorohexyl) ethanethiol (C6F13-C2H4 SH)
- 50 g of tertiobutanol
0.24 g of 4,4'-azo-bis-cyanopentanoic acid solution S2: 113.6 g (1.6 mole) of acrylamide
- 28.8 g (0.4 mole) of acrylic acid
330 g of tertiobutanol
At the end of the introduction of the two solutions S1 and S2, 0.03 g of 4,4'-azo-bis-cyanopentanoic acid is added and the temperature is maintained at 80 ° C. for 2 hours. 256 g of tert-butanol are distilled off, then 500 g of water are added and 202 g of the water / tert-butanol azeotrope are distilled off. 680 g of a solution (A6) at 22% solids content of the fluorinated telomer of formula above are thus obtained.

A7 = 20% aqueous solution of the fluorinated telomer of formula:
Rf3 - C2H4 - S - [CH2-CH (CONH2) 16 - [CH2-CH (COOH)] 4 - H prepared as the solution A6, but replacing the 38 g of 2- (perfluorohexyl) ethanethiol with 52 g (0). 1 mol) 2- (perfluoroalkyl) ethanethiols of formula:
Rf3-C2H4-SH
B1 = polyacrylamide in the form of a powder with 100% active ingredient prepared according to the following procedure:
In a one liter reactor equipped with a thermometer, a reflux condenser, a nitrogen inlet and a mechanical stirrer, 35.5% (0.5 mole) of acrylamide is dissolved in 420 ml of acetonitrile. Stirring is started, then the reaction medium is brought to 80 ° C. under nitrogen circulation. A solution of 1.4 g (0.005 mol) of 4,4'-azo-bis (4-cyanopenanoic acid) in 40 ml of acetonitrile is then introduced into the reactor. A white precipitate forms rapidly and the reaction medium is maintained at 80 ° C. for 30 minutes until the end of the polymerization The polymer is recovered by filtration, washed with acetonitrile and with acetone and then dried. polyacrylamide B1 in powder form with 100% active ingredient.

 B2 = polyacrylamide in powder form with 100% active ingredient prepared according to the same procedure as B1, but using 4.2 g (0.015 mole) of 4,4'-azo-bis (4-cyanopentanoic acid) with place of 1.4 g.

 B3 = polyacrylamide in powder form with 100% active ingredient prepared according to the same procedure as B1, but replacing the 1.4 g of 4,4'-azo-bis- (4-cyanopentanoic acid) with 0.82 g (0.005 mol) of azobis-isobutyronitrile.

 B4 = 15% aqueous solution of the hydrophilic polymer which is sold under the name DS51A by the company SNF FLOERGER and whose molar composition is 95% acrylamide and 5% N, N, N-trimethylaminoethyl acrylate methylsulfate.

 B5 = hydrophilic polymer in powder form with 100% active material prepared according to the same procedure as B3, but replacing the 35.5 g of acrylamide with a mixture comprising 33.7 g (0.475 mole) of acrylamide and 4.84 g (0.025 mole) of N, N, N-trimethylaminoethyl acrylate chloride.

CH2 = CH - COO - C2H4 - N + (CH3) 3, C
B6 = hydrophilic polymer in the form of a powder with 100% active material prepared according to the same procedure as B3, but replacing the 35.5 g of acrylamide with a mixture comprising 32 g (0.45 mole) of acrylamide and 9.7 g (0.05 mole) of N, N, N-trimethylaminoethyl acrylate chloride.

 B7 = polyacrylamide in powder form with 100% active ingredient prepared according to the same procedure as B3, but replacing the 35.5 g of acrylamide with a mixture comprising 34.4 g (0.485 mole) of acrylamide and 2 9 g (0.015 mol) of N, N, N-trimethylaminoethyl acrylate chloride.

 B8 = polyacrylamide in powder form with 100% active ingredient prepared according to the same procedure as B7, but replacing acetonitrile with a mixture comprising 97% by volume of acetonitrile and 3% by volume of water.

 Bg = polyacrylamide in powder form with 100% active material prepared according to the same procedure as B7, but replacing acetonitrile with a mixture comprising 95% by volume of acetonitrile and 5% by volume of water.

 B10 = polyacrylamide in powder form with 100% active ingredient prepared according to the same procedure as B7, but replacing acetonitrile with a mixture comprising 92% by volume of acetonitrile and 8% by volume of water.

 B11 = polyacrylamide in powder form with 100% active ingredient prepared according to the same procedure as B7, but replacing acetonitrile with isopropanol.

 B12 = polyacrylamide in powder form with 100% active ingredient prepared according to the same procedure as B7, but replacing acetonitrile with a mixture comprising 97% by volume of isopropanol and 3% by volume of water.

 B13 = polyacrylamide in powder form with 100% active ingredient prepared according to the same procedure as B7, but replacing acetonitrile with a mixture comprising 95% by volume of isopropanol and 5% by volume of water.

 B14 = polyacrylamide in powder form with 100% active ingredient prepared according to the same procedure as B7, but replacing acetonitrile with a mixture comprising 90% by volume of isopropanol and 10% by volume of water and using 0.25 g (0.0015 mole) of azobis-isobutyronitrile.

 B15 = polyacrylamide in the form of a 100% active substance powder prepared according to the same procedure as B7 but replacing acetonitrile with isopropanol and using 0.25 g (0.0015 mole) of azo-bis- isobutyronitrile.

 B16 = 15% aqueous solution of a polyacrylamide marketed under the name RS 7-22 by SNF FLOERGER.

B17 = polyvinyl alcohol marketed in the form of a powder containing 100% of active substance under the name Rhodoviol 4-125 by the company RHONE
Poulenc.

 B18 = polyvinyl alcohol marketed in the form of a powder containing 100% of active ingredient under the name Mowiol 22-88 by the company Hoechst.

EXAMPLE 1
Mixed at room temperature and with gentle stirring:
10 parts of a 30% aqueous dodecylamidopropylbetaine solution of formula:
CH3 (CH2) 10 - CONH - CH2CH2CH2 - N + (CH3) 2CH2COO-
7 parts of a 27% hydroalcoholic solution of the fluorinated behen of formula:
C6F13 - CH2CH2 - SO2NH - CH2CH2CH2 - N + (CH3) 2CH2COO-
- 20 parts of butyl diglycol
- 15 parts of A1 solution
- 1 part of B1 powder
then it is made up to 100 by addition of 47 parts of water and adjusted to pH 7 by
addition of diethanolamine. This gives a polyvalent emulsifier according to the invention
tion.

Subject to the tests described above, this foam concentrate leads to
following maneuvers:
- Expansion: 9.5
- Spread on cyclohexane: 75%
- Stability of the foam on polar liquid: 140 seconds
- Fire extinguishing efficiency on polar liquid:
Extinguishing time: 75 seconds
Foam flow: 38 kid
Mass of spilled foam: 48 g
EXAMPLES 2 to 4
A series of polyvalent fire-fighting emulsifiers according to the invention is prepared by proceeding as in Example 1, but replacing the constituents A1 and
B1 by other components in accordance with the invention, the nature and amount of which in the emulsifier are indicated in the following table.

<Tb>

Example <SEP> Solution <SEP> of <SEP> fluorinated telomer <SEP><SEP> Hydrophilic <SEP> Polymer
<tb><SEP> Nature <SEP> Quantity <SEP> Nature <SEP> Quantity
<tb><SEP> 2 <SEP> A5 <SEP> 22.5 <SEP> B2 <SEP> 2.0
<tb><SEP> 3 <SEP> As <SEP> 20.5 <SEP> B2 <SEP> 1.0
<tb><SEP> 4 <SEP> 2 <SEP> 1 <SEP> 15 <SEP> 3 <SEP> 1.0
<Tb>
Subject to the tests described above, these emulsifiers lead to the following performances:

<tb><SEP> Effectiveness <SEP> quenching <SEP> on <SEP> liquid
<tb> Emulsifier <SEP> Fokon- <SEP><SEP> Ether <SEP> Stability <SEP> of <SEP> polar
<tb><SEP> of <SEP><SEP> on <SEP><SEP> Foam <SEP> Time <SEP> Flow <SEP> of <SEP> Mass <SEP> of
<tb> example <SEP> cyclohexane <SEP> on <SEP> liquid <SEP> of extinguishing- <SEP> foam <SEP> foam
<tb><SEP> polar <SEP> tion <SEP> (g / min) <SEP> spilled
<tb><SEP> (seconds) <SEP> (seconds) <SEP> (9) <SEP>
<tb><SEP> 2 <SEP> 9.4 <SEP> 33 <SEP> seconds <SEP> 100 <SEP> 135 <SEP> 32 <SEP> 72
<tb><SEP> 3 <SEP> 10.2 <SEP> 9 <SEP> seconds <SEP> 510 <SEQ> 105 <SE> 38 <SEP> 67
<tb><SEP> 4 <SEP> 9.3 <SEP> 80% <SEP> 810 <SEP> 100 <SEP> 36 <SEP> 60
<tb> EXAMPLE5
Mixed at room temperature and with gentle stirring:
10 parts of a 45% aqueous solution of sodium (C 8 and C 10) alkyl sulphate sold under the name Sulfetal 4069 by the company
ZSCHIMMER & SCHWARTZ,
7 parts of a 40% hydroalcoholic solution of fluorinated amine oxide having the formula:
C6F13 - CH2CH2 - SO2NH - CH2CH2CH2 - N (CH3) 2 O
- 20 parts of butyl diglycol
- 15 parts of A2 solution
- 1 part of powder B2 and then complete to 100 by addition of 47 parts of water and adjusted to pH 7 by addition of diethanolamine. This gives a polyvalent emulsifier according to the invention.

Subject to the tests described above, this foam concentrate leads to the following performances:
- Partitioning: 11.0
- Spread on cyclohexane: 21 seconds
- Stability of the foam on polar liquid: 750 seconds
- Fire extinguishing efficiency on polar liquid:
Extinguishing time: 100 seconds
Foam flow: 36 gimin
Mass of spilled foam: 60 g
EXAMPLE 6
Mixed at room temperature and with gentle stirring:
5 parts of a 30% aqueous solution of N-lauryl-N, N-dimethyl amine oxide sold under the name Rewominox L408 by the company
WITCO
5 parts of the fluorinated betaine solution used in Example 1
- 15 parts of butyl diglycol
- 22.5 parts of A3 solution
- 1 part of B3 powder and then complete to 100 by addition of 51.5 parts of water and adjusted to pH 7 by addition of diethanolamine. This gives a polyvalent emulsifier according to the invention.

Subject to the tests described above, this foam concentrate leads to the following performances:
- Expansion: 9.5
- Spread on cyclohexane: 75%
- Stability of the foam on polar liquid: 130 seconds
- Fire extinguishing efficiency on polar liquid:
Extinguishing time: 150 seconds
Foam flow rate: 32 g / min
Mass of spilled foam: 80 g
EXAMPLES 7 to 30
A series of polyvalent fire-fighting emulsifiers according to the invention is prepared, proceeding as in Example 6, but replacing the constituents A1 and
B1 by other constituents according to the invention, the nature and quantity of which in the emulsifier are indicated in the following table:

<tb><SEP> Solution <SEP> of <SEP> fluorinated telomer <SEP><SEP> Hydrophilic <SEP> Polymer
<tb> Examples
<tb><SEP> Nature <SEP> Quantity <SEP> Nature <SEP> Quantity
<tb><SEP> 7 <SEP> A2 <SEP> 15 <SEP> B16 <SEP> 6.7
<tb><SEP> 8 <SEP> A4 <SEP> 22.5 <SEP> B17 <SEP> 1
<tb><SEP> 9 <SEP> A7 <SEP> 22.5 <SEP> B18 <SEP> 0.5
<tb><SEP> 10 <SEP> A2 <SEP> 15 <SEP> B <SEP> 1
<tb><SEP> 11 <SEP> A2 <SEP> 15 <SEP> B <SEP> 1
<tb><SEP> 12 <SEP> A2 <SEP> 15 <SEP> B3 <SEP> 1
<tb><SEP> 13 <SEP> A2 <SEP> 12.5 <SEP> B <SEP> 6.7
<tb><SEP> 14 <SEP> A2 <SEP> 12.5 <SEP> B <SEP> 20
<tb><SEP> 15 <SEP> A2 <SEP> 5 <SEP> B <SEP> 6.7
<tb><SEP> 16 <SEP> A2 <SEP> 12.5 <SEP> B4 <SEP> 1
<tb><SEP> 17 <SEP> A2 <SEP> 12.5 <SEP> B4 <SEP> 3
<tb><SEP> 18 <SEP> A2 <SEP> 12.5 <SEP> B4 <SEP> 5
<tb><SEP> 19 <SEP> A2 <SEP> 12.5 <SEP> B4 <SEP> 10
<tb><SEP> 20 <SEP> A2 <SEP> 12.5 <SEP> B4 <SEP> 13.3
<tb><SEP> 21 <SEP> A2 <SEP> 15 <SEP> B4 <SEP> 6.67
<tb><SEP> 22 <SEP> A2 <SEP> 17 <SEP> B7 <SEP> 0.45
<tb><SEP> 23 <SEP> A2 <SEP> 17 <SEP> B8 <SEP> 0.45
<tb><SEP> 24 <SEP> A2 <SEP> 17 <SEP> Bg <SEP> 0.45
<tb><SEP> 25 <SEP> A2 <SEP> 17 <SEP> B10 <SEP> 0.45
<tb><SEP> 26 <SEP> A2 <SEP> 17 <SEP> B11 <SEP> 0.45
<tb><SEP> 27 <SEP> A2 <SEP> 17 <SEP> B12 <SEP> 0.45
<tb><SEP> 28 <SEP> A2 <SEP> 17 <SEP> B13 <SEP> 0.45
<tb><SEP> 29 <SEP> A2 <SEP> 17 <SEP> B14 <SEP> 0.45
<tb><SEP> 30 <SEP> A2 <SEP> 17 <SEP> B15 <SEP> 0.45
<Tb>
Subject to the tests described above, these emulsifiers lead to the following performances:

<tb><SEP> Stability <SEP> of <SEP> Effectiveness <SEP> quenching <SEP> on <SEP> liquid <SEP> polar
<tb> Emulsifier <SEP> Foison- <SEP> Etale- <SEP> the <SEP> Foam
<tb><SEP> of <SEP> ment <SEP> ment <SEP> on <SEP> on <SEP> liquid <SEP> Time <SEP> Flow <SEP> of <SEP> - <SEP> Mass <SEP> of
<tb> example <SEP> cyclohexa <SEP> polar <SEP> extinction <SEP> foam <SEP> foam
<tb><SEP> no <SEP> (seconds) <SEP> (seconds) <SEP> (g / min) <SEP> spilled <SEP> (g)
<tb><SEP> 7 <SEP> 8.5 <SEP> 80% <SEP> 300 <SEP> 123 <SEP> 35 <SEP> 72
<tb><SEP> 8 <SEP> 9.5 <SEP> 40% <SEP> 105 <SEP> 85 <SEP> 36 <SEP> 51
<tb><SEP> 9 <SEP> 8.2 <SEP> 40% <SEP> 180 <SEP> 58 <SEP> 36 <SEP> 35
<tb><SEP> 10 <SEP> 10.0 <SEP> 95% <SEP> 2220 <SEP> 40 <SEP> 36 <SEP> 24
<tb><SEP> 11 <SEP> 9.8 <SEP> 95% <SEP> 2340 <SE> 41 <SEP> 33 <SEP> 23
<tb><SEP> 12 <SEP> 9.3 <SEP> 95% <SEP> 1200 <SEP> 54 <SEP> 36 <SEP> 32
<tb><SEP> 13 <SEP> 9.8 <SEP> 30 <SEP> 2000 <SEP> 34 <SEP> 34 <SEP> 22
<tb><SEP> seconds
<tb><SEP> 14 <SEP> 9.9 <SEP> 65% <SEP> 3600 <SE> 40 <SEP> 36 <SEP> 24
<tb><SEP> 15 <SEP> 10.0 <SEP> 25 <SEP> 960 <SEP> 110 <SEP> 36 <SEP> 66
<tb><SEP> seconds
<tb><SEP> 16 <SEP> 8.2 <SEP> 95% <SEP> 600 <SEP> 40 <SEP> 34 <SEP> 23
<tb><SEP> 17 <SEP> 9.0 <SEP> 85% <SEP> 660 <SE> 40 <SE> 35 <SEP> 23
<tb><SEP> 18 <SEP> 9.3 <SEP> 95% <SEP> 1860 <SE> 40 <SEP> 31 <SEP> 21
<tb><SEP> 19 <SEP> 9.3 <SEP> 35 <SEP> 1920 <SE> 40 <SEP> 36 <SEP> 27
<tb><SEP> seconds
<tb><SEP> 20 <SEP> 9.4 <SEP> 45 <SEP> 3000 <SEP> 42 <SEP> 34 <SEP> 24
<tb><SEP> seconds
<tb><SEP> 21 <SEP> 8.5 <SEP> 90% <SEP> 3300 <SEQ> 54 <SEP> 35 <SEP> 32
<tb><SEP> 22 <SEP> 9, 8 <SEP> 43 <SEP> 1560 <SEP> 43 <SEP> 36 <SEP> 26
<tb><SEP> seconds
<tb><SEP> 23 <SEP> 9.5 <SEP> 80% <SEP> 1800 <SEP> 37 <SEP> 36 <SEP> 22
<tb><SEP> 24 <SEP> 9.0 <SEP> 36 <SEP> 1620 <SEP> 43 <SEP> 36 <SEP> 26
<tb><SEP> seconds
<tb><SEP> 25 <SEP> 9.8 <SEP> 20 <SEP> 2400 <SEP> 40 <SEP> 36 <SEP> 24
<tb><SEP> seconds
<tb><SEP> 26 <SEP> 8.0 <SEP> 90% <SEP> 240 <SEP> 83 <SEP> 1 <SEP> 36 <SEP> 50
<tb><SEP> 27 <SEP> 8.5 <SEP> 26 <SEP> 290 <SE> 66 <SEP> 36 <SEP> 40
<tb><SEP> seconds
<tb><SEP> 28 <SEP> 9.4 <SEP> 25 <SEP> 330 <SEP> 62 <SEP> 36 <SEP> 37
<tb><SEP> seconds
<tb><SEP> 29 <SEP> 9.0 <SEP> 90% <SEP> 840 <SEP> 55 <SEP> 36 <SEP> 33
<tb><SEP> 30 <SEP> 8.0 <SEP> 19 <SEP> 1860 <SEP> 52 <SEP> 36 <SEP> 31
<tb><SEP> seconds
<Tb>
EXAMPLE 31 COMPARATIVE
The procedure is as in Examples 6 to 30, but by eliminating the fluorinated telomer and the hydrophilic polymer. An emulsifier which does not conform to the invention is obtained which is subjected to the tests of stability of the foam and extinguishing efficiency on polar liquid. This emulsifier leads to the following performances on polar liquid:
- Stability of the foam on polar liquid: immediate disappearance
- Fire extinguishing efficiency on polar liquid:
Extinguishing time:> 300 seconds
Foam flow rate: 38 g / min
Mass of spilled foam:> 190 g
The absence of fluoro telomer and hydrophilic polymer does not allow to obtain a stable foam on polar liquid; this disappears immediately and during the test of fire extinguishing performance on polar liquid, the extinction time is very long and the amount of foam spilled is also high.

EXAMPLES 32 to 35 COMPARATIVES
A series of emulsifiers not according to the invention is prepared. The procedure is as in Examples 6 to 30, but by removing either the fluorinated telomer or the hydrophilic polymer. The amounts of fluorinated telomer or hydrophilic polymer are indicated in the following table:

<tb> Example <SEP> Solution <SEP> of <SEP> fluorinated telomer <SEP><SEP> Hydrophilic <SEP> Polymer
<tb><SEP> Nature <SEP> Quantity <SEP> Nature <SEP> | <SEP> Quantity
<tb> 32 <SEP> 32 <SEP> A2 <SEP> 15 <SEP> not <SEP> of <SEP> hydrophilic <SEP> polymer
<tb><SEP> 33 <SEP> A2 <SEP> 10 <SEP> not <SEP> of <SEP> hydrophilic <SEP> polymer
<tb><SEP> 34 <SEP> not <SEP> from <SEP> fluorinated telomer <SEP><SEP> B2 <SEP> 1
<tb><SEP> 35 <SEP> not <SEP> from <SEP> telomer <SEP> fluorinated <SEP> B1 <SEP> 1
<Tb>
Subject to the tests described above, these emulsifiers lead to the following performances on polar liquid:

<tb><SEP> Stability <SEP> of <SEP> the <SEP> Effectiveness <SEP> quenching <SEP> on <SEP> liquid
<tb><SEP> Emulsifier <SEP> Foam <SEP> on <SEP> Polar
<tb><SEP> of <SEP> L <SEP> liquid <SEP> Time <SEP> Flow <SEP> of <SEP> Mass <SEP> of
<tb><SEP> example <SEP> polar <SEP> extinction <SEP> foam <SEP> I <SEP> foam
<tb> comparative <SEP> (seconds) <SEP> (seconds) <SEP> (g / min) <SEP> spilled
<tb><SEP> (g)
<tb><SEP> 32 <SEP> 70 <SEP> 156 <SEP> 34 <SEP> 88
<tb><SEP> 33 <SEP> 60 <SEP> 185 <SEP> 36 <SEP> 111
<tb><SEP> 34 <SEP> disappear <SEP> immediately <SEP> 297 <SEP> 38 <SEP> 188
<tb><SEP> diate
<tb><SEP> 35 <SEP> disappear <SEP> immediately <SEP> 315 <SEP> 36 <SEP> 189
<tb><SEP> diate
<Tb>
The absence of one of the two essential elements of the invention leads to
lower polar performance. It is found that the non
according to the invention containing the fluorinated telomer alone (comparative examples 32
and 33) still have some effect on the stability of the foam and on
extinguishing efficacy on polar liquid compared to the concentrate of the example compa
Ratif 31, but this effect is insufficient. On the other hand, the hydrophilic polymer alone
(Comparative Examples 34 and 35) provides no polar liquid performance.

EXAMPLES 36 to 38
A series of extinction tests is carried out according to standard NF S 60225 - 0.25 m 2 acetone focus reference test. The test conditions are as follows:
- dilution rate in city water = 3%
- Precombustion time of acetone = 120 seconds
- application time of the foam = 120 seconds
The results of the extinction tests are reported in the following table:

<tb><SEP> Emulsifier <SEP> OFF <SEP> Time <SEP> (seconds) <SEP><SEP> Time <SEP> Re-Ignition
<tb><SEP> Example <SEP> of <SEP> | <SEP> (seconds)
<tb><SEP> the <SEP> sample | <SEP> 90% <SEP> 99% <SEP><SEP> Extinguishing <SEP> Start <SEP> 80%
<tb><SEP> total
<tb><SEP> 36 <SEP> 10 <SEP> 25 <SEP> 35 <SEP> 80 <SEP> 520 <SEP> 765
<tb><SEP> 37 <SEP> 13 <SEP> 22 <SEP> 30 <SEP> 70 <SEP> 510 <SEP> 720
<tb> 38 <SEP> 14 <SEP> 1 <SEP> 35 <SEP> | <SEP> 50 <SEP> 75 <SEP> | <SEP> 390 <SEP> 1 <SEP> 300
<Tb>
EXAMPLES 39 to 41
A series of emulsifiers according to the invention is prepared according to the procedure of Example 6, but by varying the amounts of fluorometric telomer solution A2 and of hydrophilic polymer solution B4 in proportions indicated in the following table:

<tb> Example <SEP> I <SEP> Quantity <SEP> of <SEP> solution <SEP> of <SEP> Quantity <SEP> of <SEP> solution <SEP> of
<tb><SEP> telomer <SEP> fluorinated <SEP> A2 <SEP> polymer <SEP> hydrophilic <SEP> B <SEP>
<tb><SEP> 39 <SEP> 20 <SEP> 3
<tb><SEP> 40 <SEP> 15 <SEP> 5
<tb><SEP> 41 <SEP> 20 <SEP> 6.7
<Tb>
With the three emulsifiers above, a series of extinction tests are carried out according to standard NF S 60225 under the same conditions as in Examples 36 to 38.

The results of the extinction tests are reported in the following table:

<tb><SEP> OFF <SEP> time <SEP><SEP> time of <SEP> re-ignition
<tb> Emulsifier <SEP> (seconds) <SEP> (seconds)
<tb><SEP> of <SEP> 90% <SEP> 99% <SEP> Extinguishing <SEP> Start <SEP> 80%
<tb> the total <SEP> example
<tb><SEP> 39 <SEP> 20 <SEP> 30 <SEP> 65 <SEP> 600 <SEP> 735
<tb><SEP> 40 <SEP> 40 <SEP><SEP> 20 <SEP> 30 <SEP> 67 <SEP> 510 <SEP> 660 <SEP>
<tb><SEP> 41 <SEP> 41 <SEP> 25 <SEP> 35 <SEP> 73 <SEP> 530 <SEP> 745
<Tb>
EXAMPLES 42 to 45
A C1 solution containing 25.5% of active substance is prepared by mixing at room temperature and with gentle agitation 70 parts of solution A2 and 30 parts of solution B4. On the other hand, we have various synthetic emulsifiers
Commercial AFFFs that can only be used on hydrocarbon fires. Dilution rates when using these emulsifiers are specified by the manufacturers, ie:
- Tridol S6 (WATER AND FIRE) 6% dilutable foam concentrate
- Light Water FC 206 (3M) 6% dilutable foam concentrate
- Aquafilm 6 (AUXQUIMIA) 6% dilutable foam concentrate
- Aquafilm 1 (AUXQUIMIA) 1% dilutable foam concentrate
From these AFFF emulsifiers, polyvalent emulsifiers according to the invention are prepared by mixing the appropriate amounts of AFFF emulsifier and C1 solution. The emulsifiers according to the invention resulting from these mixtures are listed in the following table:

<tb><SEP> Emulsifier <SEP> AFFF <SEP> used <SEP><SEP> Amount of <SEP> I <SEP><SEP><SEP> Dilution Rate
<tb> Example <SEP> of <SEP> the foam concentrate
<tb><SEP> Name <SEP> of <SEP> the emulsifier <SEP> Quantity <SEP> solution <SEP> C1 <SEP> final <SEP> (%)
<tb><SEP> 42 <SEP> Tridol <SEP> S6 <SEP> 90 <SEP> 10 <SEP> 6
<tb><SEP> 43 <SEP> Light <SEP> Water <SEP> FC <SEP> 206 <SEP> 90 <SEP> 10 <SEP> 6
<tb><SEP> 44 <SEP> Aquafilm <SEP> 6 <SEP> 90 <SEP> 10 <SEP> 6
<tb><SEP> 45 <SEP> Aquafilm <SEP> 1 <SEP> 60 <SEP> 40 <SEP> 1
<Tb>
The polyvalent emulsifers thus obtained are subjected to the tests described above but by diluting them with tap water at the rates indicated in the table above instead of the 3% mentioned in the description of the tests. They lead to the following performances on polar liquid:

<tb> Emulsifier <SEP> Stability <SEP> of <SEP><SEP> Efficiency <SEP> quenching <SEP> suf <SEP> liquid <SEP> polar
<tb><SEP> of <SEP> Foam <SEP> on <SEP> Time <SEP> Flow <SEP> of <SEP> Mass <SEP> of
<tb> example <SEP> liquid <SEP> polar <SEP> extinction <SEP> foam <SEP> foam
<tb><SEP> (seconds) <SEP> (seconds) <SEP> (g / min) <SEP> spilled <SEP> (g)
<tb><SEP> 42 <SEP> 1920 <SEP> 46 <SEP> 35 <SEP> 27
<tb><SEP> 43 <SEP> 1260 <SEP> 38 <SEP> 36 <SEP> 23
<tb><SEP> 44 <SEP> 1740 <SEP> 45 <SEP> 36 <SEP> 27
<tb><SEP> 45 <SEP> 2040 <SEP> 45 <SEP> 35 <SEP> 26
<Tb>
EXAMPLES 46 to 48
A C2 solution containing 29% of active substance is prepared by mixing at room temperature and with moderate stirring 94 parts of solution A2 and 6 parts of solution B4. On the other hand, there are various protein hydrolysates used as foaming bases for the development of protein emulsifiers.

These hydrolysates consist of hydrolysed protein residues in aqueous solution. The contents of active ingredient of these hydrolysates are adapted according to the dilution ratios specified by the manufacturers:
- WATER AND FIRE: 6% dilutable hydrolyzate containing a glycol ether
- CHUBB FIRE: dilutable 3% hydrolyzate containing a glycol ether
- TOTAL WALTHER: dilutable 6% hydrolyzate without glycol ether
From these protein hydrolysates, polyvalent emulsifiers according to the invention are prepared by mixing the appropriate amounts of hydrolyzate, of solution
C2, fluorinated betaine used in Example 1 and optionally butyl diglycol.

The emulsifiers according to the invention resulting from the mixtures are listed in the following table:

<tb> Exem- <SEP> Hydrolysate <SEP> of <SEP> Proteins <SEP> Quantity <SEP> Quantity <SEP> Quantity <SEP> Rate <SEP> of
<tb><SEP> ple <SEP> used <SEP> of <SEP> of <SEP> of <SEP> butyl <SEP> dilution <SEP> of
<tb><SEP> solution <SEP> solution <SEP> diglycol <SEP> emulsifier
<tb><SEP> C2 <SEP> of <SEP> final
<tb><SEP> Betaine
<tb><SEP> Name <SEP> of <SEP> manufacturer <SEP> | <SEP> Quantity <SEP> fluorinated <SEP> (%)
<tb><SEP> 46 <SEP> WATER <SEP> AND <SEP> FIRE <SEP> 91.5 <SEP> 4.5 <SEP> 4 <SEP> 0 <SEP> 6
<tb><SEP> 47 <SEP> CHUBB <SEP> FIRE <SEP> 83 <SEP> 9 <SEP> 8 <SEP> 0 <SEP> 3
<tb><SEP> 48 <SEP> TOTAL <SEP> 86.5 <SEP> 4.5 <SEP> 4 <SEP> 5 <SEP> 6
<tb><SEP> WALTHER
<Tb>
The polyvalent emulsifers thus obtained are subjected to the tests described above by diluting them with tap water at the rates indicated in the table above. They lead to the following performances on polar liquid:

<tb><SEP> Effectiveness <SEP> quenching <SEP> on <SEP> liquid
<tb><SEP> Emulsifier <SEP> Stability <SEP> of <SEP> the <SEP> polar
<tb> of <SEP> Example <SEP> Foam <SEP> on <SEP> Time <SEP> Flow <SEP> of <SEP> Mass <SEP> of
<tb><SEP> liquid <SEP> polar <SEP> extinguishing <SEP> foam <SEP> foam
<tb><SEP> (seconds) <SEP> (seconds) <SEP> (g / min) <SEP> spilled <SEP> (g)
<tb><SEP> 46 <SEP> 1200 <SE> 67 <SEP> 35 <SEP> 39
<tb><SEP> 47 <SEP> 1400 <SEP> 45 <SEP> 36 <SEP> 27
<tb><SEP> 48 <SEP> 2100 <SEP> 60 <SEP> 38 <SEP> 38
<Tb>
EXAMPLE 49
Mixed at room temperature and with gentle stirring:
5 parts of a 30% aqueous solution of N-lauryl-N, N-dimethyl amine oxide sold under the name Rewominox L408 by the company
WITCO
5 parts of a 27% hydroalcoholic solution of a mixture of fluorinated betaines having the formula: Rf5-CH2CH2-SO2NH-CH2CH2CH2-N + (CH3) 2CH2COO-
- 15 parts of butyl diglycol
- 17 parts of A2 solution
3 parts of solution B4 are then added to 100 parts by addition of 55 parts of water and adjusted to pH 7 by addition of diethanolamine. This gives a polyvalent emulsifier according to the invention.

Subject to the tests described above, this foam concentrate leads to the following performances:
- Spreading: 8.4
- Spread on cyclohexane: 32 seconds
Stability of the foam on polar liquid: 3840 seconds
- Fire extinguishing effectiveness on polar fluid
Extinguishing time: 38 seconds
Foam flow rate: 36 g / min
Mass of spilled foam: 23 g
EXAMPLE 50
In a one-liter reactor equipped with a thermometer, a reflux condenser, a nitrogen inlet and a mechanical stirrer, 68.8 g (0.97 moles) of acrylamide are dissolved and 5.8 g (0.03 mol) of N, N, N-trimethylaminoethyl acrylate chloride in 420 ml of demineralized water. The agitation is started. The reaction medium is brought to a temperature of 40 ° C. under nitrogen circulation A solution of 0.675 g (0.0025 mol) of potassium persulphate (K 2 S 2 O 8) is prepared in 20 ml of demineralized water and a solution of 0.444 g (0.002 mole) of potassium metabisulphite (K 2 S 2 O 5) in 20 ml of demineralized water After 30 minutes, the potassium persulfate solution is poured into the reactor and the solution of potassium metabisulphite is poured in after two minutes.

 The temperature then increases to 55 ° C. and then decreases, when the temperature reaches 50 ° C., it is heated to 80 ° C. and the reaction medium is maintained at 80 ° C. for 30 minutes and then allowed to cool to room temperature. .

536 g of a C3 aqueous solution containing about 15% by weight of a copolymer whose molar composition is 97% of acrylamide and 3% of chloride are obtained.
N, N, N-trimethylaminoethyl acrylate.

EXAMPLE 51
The procedure is as in Example 50, but during the polymerization, the amounts of incorporated initiators are as follows:
- 0.338 g (0.00125 moles) of potassium persulfate
0.222 g (0.001 mol) of potassium metabisulphite.

 An aqueous C4 solution of about 15% by weight of a copolymer of acrylamide and N, N, N-trimethylaminoethyl acrylate is obtained.

EXAMPLE 52
The procedure is as in Example 50, but during the polymerization is added in the reactor:
2.5 ml of an aqueous buffer solution containing 0.026 mole / liter of potassium dihydrogenphosphate (KH 2 PO 4) and 0.041 mole / liter of sodium hydrogenphosphate (Na 2 HPO 4), and the amounts of incorporated initiators are as follows:
- 0.162 g (0.0006 mol) of potassium persulfate,
0.11 g (0.0005 mol) of potassium metabisulphite.

 An aqueous C5 solution of about 15% by weight of a copolymer of acrylamide and N, N, N-trimethylaminoethyl acrylate is obtained.

EXAMPLE 53
The procedure is as in Example 50, but during the polymerization is added in the reactor:
10 ml of an aqueous buffer solution containing 0.026 mol / liter of potassium dihydrogenphosphate (KH2PO4) and 0.041 mol / liter of sodium hydrogenphosphate (Na2HPO4),
0.57 g (0.005 mol) of sodium mercaptoacetate, and the amounts of incorporated initiators are as follows:
- 0.162 g (0.0006 mol) of potassium persulfate,
0.11 g (0.0005 mol) of potassium metabisulphite.

 An aqueous C6 solution of about 15% by weight of a copolymer of acrylamide and N, N, N-trimethylaminoethyl acrylate is obtained.

EXAMPLE 54
The procedure is as in Example 50, but during the polymerization is added in the reactor:
2.7 ml of an aqueous buffer solution containing 0.026 mol / liter of potassium dihydrogenphosphate (KH2PO4) and 0.041 mol / liter of sodium hydrogenphosphate (Na2HPO4),
1.14 g (0.01 mole) of sodium mercaptoacetate, and the amounts of incorporated initiators are as follows:
0.243 g (0.0009 mol) of potassium persulfate,
0.11 g (0.0005 mol) of potassium metabisulphite.

 An aqueous C7 solution of about 15% by weight of a copolymer of acrylamide and N, N, N-trimethylaminoethyl acrylate is obtained.

EXAMPLES 55 to 59
Solutions C3 to C7 of the hydrophilic polymers prepared in Examples 50 to 54 are used to prepare emulsifiers according to the invention.

For this, mix at room temperature and with moderate agitation:
5 parts of a 30% aqueous solution of N-lauryl-N, N-dimethyl amine oxide sold under the name Rewominox L408 by the company WITCO
5 parts of the fluorinated betaine solution used in Example 1
- 15 parts of butyl diglycol
- 17 parts of A2 solution
- 3 parts of one of the solutions C3 to C7 prepared above, then complete to 100 parts by addition of 55 parts of water and adjusted to pH 7 by addition of a normal aqueous solution of sodium hydroxide . This gives a polyvalent emulsifier according to the invention.

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

Solution <SEP> Spreading <SEP> on <SEP> Stability <SEP> of <SEP><SEP> Efficiency <SEP> quenching <SEP> on <SEP> liquid <SEP> polar
<tb> Example <SEP> used <SEP> Weather <SEP> cyclohexane <SEP> Foam <SEP> on <SEP> Time <SEP> Flow <SEP> of <SEP> Mass <SEP> of
<tb> nt <SEP> (seconds) <SEP> liquid <SEP> polar <SEP> extinction <SEP> foam <SEP> foam
<tb> (seconds) <SEP> (seconds) <SEP> (g / min) <SEP> spilled <SEP> (g)
<tb> 55 <SEP> C3 <SEP> 8.9 <SEP> 18 <SEP> 1380 <SE> 64 <SEP> 36 <SEP> 39
<tb> 56 <SEP> C4 <SEP> 8.4 <SEP> 14 <SEP> 2100 <SEP> 55 <SEP> 36 <SEP> 33
<tb> 57 <SEP> C5 <SEP> 9.1 <SEP> 15 <SEP> 4920 <SEP> 47 <SEP> 36 <SEP> 28
<tb> 58 <SEP> C6 <SEP> 9.8 <SEP> 12 <SEP> 5700 <SEP> 41 <SEP> 36 <SEP> 25
<tb> 59 <SEP> C7 <SEP> 9.0 <SEP> 15 <SEP> 3300 <SEP> 48 <SEP> 36 <SEP> 29
<Tb>

Claims (18)

 1. Multipurpose synthetic or proteinaceous fire extinguisher, characterized in that it comprises by weight1 per 100 parts by weight of emulsifier:  (a) from 0.5 to 15 parts of at least one fluorinated telomer having a perfluoroalkyl radical and a polymerized chain consisting of units of at least one hydrophilic monomer; and  (b) from 0.03 to 10 parts of at least one non-fluorinated hydrophilic polymer obtained by radical polymerization of one or more hydrophilic monomers.  2. Emulsifier according to claim 1, wherein the polymerized chain of the fluorinated telomer (a) consists of units of a non-ionic hydrophilic monomer and optionally an anionic hydrophilic monomer.  3. Emulsifier according to claim 1 or 2, wherein the hydrophilic non-fluorinated polymer (b) is obtained by radical polymerization of at least one nonionic hydrophilic monomer and optionally at least one cationic hydrophilic monomer.  An emulsifier according to claim 2 or 3, wherein the fluorinated telomer (a) has the formula:  Rf - (CH2) k - Xm - (CH2) n - Sp - (M1) q1 (M2) q2 - Y (I) in which:  Rf represents a linear or branched chain perfluoroalkyl radical containing at least 6 carbon atoms,  k is an integer ranging from 0 to 6, but different from O if m is equal to 1,  X represents an oxygen atom or a CO2 or OCO group, equal to 1,  n is an integer ranging from 0 to 6, but different from O if m and / or p is equal to 1,  pestgaloou 1,  M1 represents an anionic hydrophilic monomer unit and M2 a nonionic hydrophilic monomer unit,  q1 and q2 are numbers whose sum is between 5 and 100, the ratio q1 / q2 being between 0 and 2,  Y represents a hydrogen atom when p is equal to 1 and an iodine, bromine or chlorine atom when p is 0.  5. Emulsifier according to claim 4, in which the radical Rf contains from 6 to 20 carbon atoms, k is equal to 0 or 2, X represents a group OCO, n is equal to 0 or 1, the sum q1 + q2 is between 10 and 50, Y is a hydrogen or iodine atom, M1 is a unit of formula:

 and M2 a unit of formula:

 in which R1 and R2, which may be identical or different, each represent a hydrogen atom or a methyl radical, Q1 represents a hydrogen atom, an alkaline metal ion or a quaternary ammonium ion, and Q2 represents an OH group or a CONR3R4 group in which the symbols R3 and R4, which are identical or different, each represent a hydrogen atom or an alkyl or hydroxyalkyl radical containing from 1 to 3 carbon atoms.  6. Emulsifier according to claim 5, wherein Q1 represents a hydrogen atom or an alkali metal ion and Q2 represents the CONH2 group.  7. Emulsifier according to one of claims 4 to 6, wherein k = 0 or 2, m = n = p = 0, and Y is an iodine atom.  8. Emulsifier according to one of claims 4 to 6, wherein k = 2, m = n = 0 or 1, p = 1, and Y is a hydrogen atom.  9. Emulsifier according to one of claims 4 to 8, wherein the ratio q1 / q2 is between 0 and 1.  10. Emulsifier according to one of claims 3 to 9, wherein the hydrophilic non-ionic monomers used in the composition of the polymer (b) are chosen from: acrylamide, methacrylamide and their derivatives corresponding to the formula :

 acrylates and methacrylates of aminoalcohols corresponding to the formula:

 in which R5 and R6, which may be identical or different, each represent a hydrogen atom or a methyl radical, R8 and R9, which may be identical or different, each represent a hydrogen atom, an alkyl or hydroxyalkyl radical containing from 1 to 3 carbon atoms, carbon, R10 and R11, which may be identical or different, each represent an alkyl or hydroxyalkyl radical containing 1 to 4 carbon atoms, B represents an alkylene or hydroxyalkylene radical containing from 1 to 4 carbon atoms;  Vinyl acetate, the polymerization being followed by hydrolysis which converts the resulting hydrophobic vinyl polyacetate into hydrophilic polyvinyl alcohol; and  the cationic hydrophilic monomers optionally entering into the composition of the polymer (b) are chosen from acrylates and methacrylates of aminoalcohols corresponding to the formula:

 in which R7 represents a hydrogen atom or a methyl radical, R12, R13 and R14, which may be identical or different, each represent an alkyl or hydroxyalkyl radical containing 1 to 4 carbon atoms, B 'represents an alkylene or hydroxyalkylene radical containing from 1 to at 4 carbon atoms, A- is any monovalent anion.  11. Emulsifier according to one of claims 3 to 10 wherein the polymer (b) is obtained by radical polymerization of a mixture of 80 to 100%, preferably 93 to 100 mol% of at least one monomer. nonionic hydrophilic and from 0 to 20%, preferably from 0 to 7%, in moles of at least one cationic hydrophilic monomer.  12. Emulsifier according to claim 10 or 11, wherein R8 and R9 represent a hydrogen atom, R10, R11, R12, R13 and R14 represent a methyl radical, B and B 'represent the divalent group -CH2-CH2-.  13. Emulsifier according to one of claims 1 to 12, characterized in that it contains 1 to 10 parts by weight of at least one fluorinated telomer (a) and 0.1 to 6 parts by weight of at least one nonfluorinated hydrophilic polymer (b) per 100 parts by weight of emulsifier, the remainder consisting of the usual ingredients of a synthetic emulsifier, preferably a synthetic emulsifier AFFF, or those of a protein emulsifier, preferably a fluoroproteinic emulsifier.  14. Emulsifier according to claim 13, characterized in that it contains from 2 to 8 parts by weight of at least one fluorinated telomer (a) and from 0.5 to 4 parts by weight of at least one non-hydrophilic polymer. fluorinated (b) per 100 parts by weight of emulsifier.  15. Use of an emulsifier according to one of claims 1 to 14 for combating hydrocarbon fires or polar liquid fires.  16. Additive for an anti-fire emulsifier characterized in that it consists esesntiellement of an aqueous solution containing by weight:  from 2 to 50% (preferably 10 to 30%) of at least one fluorinated telomer having a perfluoroalkyl radical and a polymerized chain consisting of units of at least one hydrophilic monomer, and  from 0.1 to 20% (preferably 1 to 10%) of at least one non-fluorinated hydrophilic polymer obtained by radical polymerization of one or more hydrophilic monomers.  17. Additive according to claim 16 containing a fluorinated telomer according to one of claims 4 to 9.  18. Additive according to claim 16 or 17 containing a hydrophilic polymer according to one of claims 10 to 12.