• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Surfactant mixture (M1) based on glutamate and alkyl polyglycosides, comprising an aqueous composition in combination with fluorinated surfactants; its use, in the fight against fire.
    公开号:FR3061025A1
    申请号:FR1663286
    申请日:2016-12-23
    公开日:2018-06-29
    发明作者:Marie-Francoise Gayral Chirac；Jerome Guilbot；Georges Da Costa
    申请人:Societe dExploitation de Produits pour les Industries Chimiques SEPPIC SA；
    IPC主号:
    专利说明:

    ® Agent (s): AIR LIQUIDE.
    ® NEW SURFACTANT MIXTURE, NEW COMPOSITION COMPRISING IT AND ITS USE IN EMULSERS TO FIGHT FIRES.
    @) Surfactant mixture (M 1) based on glutamate and alkyl polyglycosides, aqueous composition comprising in combination with fluorinated surfactants; its use in fire fighting.
    FR 3,061,025 - A1
    2016P00666-FR
    The subject of the present invention is a new mixture of surfactants, compositions comprising them and their use in the preparation of fire-fighting emulsifiers.
    The foams consist of a set of gas cells separated by thin layers of liquids and are formed by the juxtaposition of bubbles, more or less fine, that generates a gas dispersed in a liquid. They are generally prepared from aqueous compositions comprising at least one foaming surfactant by mixing a gas, such as, for example, air or nitrogen or carbon dioxide. Certain surfactants are known to generate foams by mixing with gases.
    It is well known to use compositions comprising at least one foaming surfactant to form foams intended to extinguish fires. We can cite four modes of action of foams in extinguishing fires: the isolation of flammable vapors and gases, cooling by the water contained in the foam, smothering the fire and the screen against the radiant heat of a fireplace. Foams, lighter than liquids, are sent to the surface of a fire or in a burning volume, and act mainly by cooling and / or smothering; in the latter case, the foams form an insulating cover, preventing the supply of oxygen (the oxidizer) to the fire and thus isolating it from the fuel.
    These foams are particularly suitable for extinguishing fires of flammable liquids, such as for example solvents, and more particularly alcohols (methanol, ethanol, propanol, butanol), amines, ketones (acetone, methyl ethyl ketone), esters (methyl acetate, ethyl acetate), hydrocarbons.
    To produce foam, it is necessary to vigorously mix pressurized water, an emulsifier and a gas (such as air, carbon dioxide or nitrogen).
    An emulsifier is a fluid which has the property of reducing the surface tension of the water with which it is mixed, allowing the formation of gas bubbles when the water, the emulsifier and the gas come into contact. Mixtures comprising foaming agents intended to produce foam for extinguishing fires are called "fire-fighting foam concentrates" and are generally sprayed onto the fire in the form of foam obtained after being mixed under pressure with water.
    Foams are characterized by their expansion rate, their expansion rate and their stability.
    2016P00666-FR
    The expansion rate (T F ) is the ratio between the volume of foam produced by a foaming composition over the volume of the foaming solution used (water and foam concentrate). Consequently, the more the expansion rate increases, the lighter the foam and its large volume, and therefore the more the projection distances of said foam decrease. In the technical field of fire fighting, we distinguish:
    - Foams known as very low expansion, for which (T F ) is less than 4; they form a gel or a film on the surface of liquids with film-forming emulsifiers, and thus help to slow down the phenomenon of evaporation;
    - So-called low expansion foams, for which (T F ) is greater than or equal to 4 and less than 20; they can be projected at great distances using mobile lances or cannons; they are stable, provide fire-resistant cover and are not very sensitive to atmospheric conditions;
    - The so-called medium expansion foams, for which (T F ) is greater than or equal to 20 and less than 200, they can be sprayed up to ten meters, they are more sensitive to bad weather and their resistance to re -inflammation is lower than that of low expansion foam. They can be used in cases where large quantities of foam are necessary when the water resources are limited, and they are also suitable for the treatment of retention of leaks or liquefied gases.
    - Foams known as high expansion, for which (T F ) is greater than or equal to 200; they are suitable for fighting fires in large volumes, but are light and can therefore be dispersed by wind. They are better suited for indoor use, for example for fires in storage tanks for hydrocarbons or polar liquids.
    As emulsifiers used in the fight against fires, there are in particular protein emulsifiers, fluoroprotein emulsifiers, emulsifiers forming floating films known as AFFF for: Aqueous Film-Forming Foam and polyvalent emulsifiers known as designation A4P, for Film Producing Agent Polyvalent Protector or ARAFFF for: Alcohol Resistant Aqueous Film-Forming Foam.
    - Protein-based foam concentrates consist of protein hydrolysates; they make it possible to obtain foams with effective resistance to re-ignition and are preferred in the fight against large installation fires in the chemical and / or petroleum industries;
    2016P00666-FR
    - AFFF foam concentrates, quickly extinguish fires caused by hydrocarbon liquids; they include non-fluorinated surfactants and fluorinated surfactants which have a very low surface tension value and consequently make it possible to produce a foam which, by decantation, forms an aqueous film floating above the surface of the hydrocarbon, which makes it possible to extinguish the fire and avoid possible re-ignition. However, they are not effective for fires caused by polar solvents, in particular alcohols, ketones and low molecular weight esters.
    ARAFF foam concentrates are used to combat polar solvent fires. They also include fluorinated surfactants, non-fluorinated surfactants and a water-soluble polymer; this polymer precipitates on contact with the polar solvent and forms a protective layer between said polar solvent and the foam.
    The presence of non-fluorinated surfactants in foam concentrates of the AFFF and ARAFF type makes it possible to achieve other characteristics useful in extinguishing the fire, such as the rapid formation of a sufficiently large volume of a sufficiently stable foam.
    The international applications published under the numbers WO 91/01160 and WO 92/15371 describe the preparation of fire-fighting emulsifiers of the AFFF and ARAFFF type containing nonionic surfactants of the alkyl polyglycoside type, marketed under the brand names "APG 300" and "APG 325", the alkyl chains of which comprising from nine to eleven carbon atoms.
    International application published under number WO 96/38204 discloses a foaming composition comprising at least one fluorinated surfactant and at least one alkyl polyglycoside hemisulfosuccinate surfactant on alkyl chains, linear or branched, comprising from six to eighteen carbon atoms.
    The American patent published under the number US 5,434,192 discloses the use of aqueous compositions comprising a polymer, a solvent, a fluorinated surfactant, and one or more non-ionic surfactants of the alkyl polyglycoside type, said composition being intended to generate a foam used for remove hydrocarbon and organic solvent vapors following an effusion.
    To obtain highly stable foams, the skilled person must combine the foaming surfactants with one or more additives which have the effect of increasing the rigidity of the gaseous cells forming the foam.
    2016P00666-FR
    French patent application published under number 2,439,230 discloses the use of fatty amines as a foaming aid, aqueous solutions of surfactants such as alkylbetaines, alkylamidobétaines, alkylsulfates or alkyl ether sulfates.
    International application published under number WO 03/035794 A1 teaches that an alkyl phosphate mono-ester improves the stability of a used in a drilling process for oil wells.
    However, foam stabilizing additives are often poorly biodegradable and are sometimes toxic, which makes them non-compliant with new environmental requirements and regulations. They thus prove to be unusable in foams intended to fight open fires, in particular in a forest environment.
    New technical solutions have recently been developed to prepare surfactant compositions generating stable foams without the addition of foam stabilizing additives. We can thus cite the international application published under publication number WO 2012/085391 A1, which discloses a method of drilling cavities in underground formations using an aqueous fluid in the form of a foam obtained by mixing d '' a gas or a mixture of gases and an aqueous solution comprising an N-acylated derivative of glutamic acid, or a salt thereof, and / or aspartic acid, or a its salts, for which the acyl radical contains from eight to eighteen carbon atoms. The foams generated by the aqueous solutions comprising such N-acyl derivatives of glutamic acid, or one of its salts, and / or aspartic acid, or one of its salts, exhibit both l advantage of forming with a short expansion time and of showing mechanical properties making them suitable for use in a step of removal of cuttings during an operation of drilling underground cavities.
    However, it has been observed by the applicant that the properties of the foams formed from aqueous solutions comprising N-acylated derivatives of glutamic acid or of a salt thereof, and / or of aspartic acid or of one of its salts, necessary for uses of fire extinctions, in particular the duration of expansion and the stability of the foam, exhibited variations making their effectiveness random.
    2016P00666-FR
    There is therefore a need to have surfactant systems capable of generating a foam having a sufficiently rapid expansion time, remaining sufficiently stable and having an expansion rate less than or equal to 20, so that they can be used in the fight against fires. .
    This is why the first object of the invention is a surfactant mixture (Mi) characterized in that it comprises per 100% of its mass:
    (i) - From 50% to 99% by mass, more particularly from 55% to 99% by mass, and even more particularly from 57% to 99% by mass of a composition (Ci) comprising for 100% of its mass:
    (a) - From 65% to 90% by mass, more particularly from 65% to 85% by mass and very particularly from 65% to 80% by mass of at least one compound of formula (I):
    R 1 -C (= O) -NH-CH (COOH) - (CH 2 ) 2 -COOH (I) in acid form, partially or totally salified in which the group Ri-C (= O) -represents an acyl radical linear or branched, saturated or unsaturated, containing from eight to eighteen carbon atoms, and (β) - From 10% to 35% by mass, more particularly from 15% to 35% by mass, and very particularly from 20% to 35 % by mass of at least one compound of formula (II):
    R 1 -C (= O) -OH (II) in acid form, partially or totally salified, in which the group Ri is as defined for formula (I), (ii) - From 1% to 50% by mass, more particularly from 1% to 45% by mass, and still more particularly from 1% to 43% by mass of a composition (C 2 ) comprising for 100% of its mass:
    (y) - From 37.5% to 100% by mass of a composition (C 3 ) or of a mixture of compositions (C 3 ), said composition (C 3 ) being represented by formula (III):
    R 3 -O- (G 3 ) P -H (III) in which R 3 represents a linear or branched, saturated or unsaturated aliphatic radical containing from twelve to sixteen carbon atoms, G 3 represents the remainder of a reducing sugar and p represents a decimal number greater than or equal to 1.05 and less than or equal to 5, said composition (C 3 ) consisting of a mixture of compounds represented by the formulas (III,), (lll 2 ), (lll 3 ) , (lll 4 ) and (lll 5 ):
    R 3 -O- (G 3 ) iH (llh), r 3 - O - (G 3 ) 2 -H (lll 2 ),
    2016P00666-FR
    R 3 -O- (G 3 ) 3 -H (lll 3 ),
    R 3 -O- (G 3 ) 4 -H (lll 4 ),
    R 3 -O- (G 3 ) 5 -H (III 5 ), in the respective molar proportions ai, a 2 , a 3 , a 4 and a 5 , such that:
    the sum: ai + a 2 + a 3 + a 4 + a 5 is equal to 1, and the sum ai + 2a 2 + 3a 3 + 4a 4 + 5a 5 is equal to p;
    (δ) - From 0% to 37.5% by mass of at least one alcohol of formula (IV):
    R 3 -OH (IV) in which R 3 is as defined for the preceding formula (III), (ε) - From 0% to 12.5% of a composition (C 4 ) or of a mixture of compositions (C 4 ), said composition (C 4 ) being represented by formula (V):
    R 4 -O- (G 4 ) q -H (V) in which R 4 represents a linear aliphatic radical, chosen from butyl radicals (nC 4 H 9 -), pentyl radical (n-CsHu-), hexyl radical (nC 6 H 13 -), the heptyl radical (nC 7 H 15 -) and the (2-ethyl hexyl) radical, G 4 represents the remainder of a reducing sugar and q represents a decimal number greater than or equal to 1, 05 and less than or equal to 5, said composition (C 4 ) consisting of a mixture of compounds represented by the formulas (V1), (V 2 ), (V 3 ), (V 4 ) and (V 5 ):
    R 4 -O- (G 4 ) iH (V1), R 4 -O- (G 4 ) 2 -H (V 2 ), R 4 -O- (G 4 ) 3 -H (V 3 ), R 4 -O- (G 4 ) 4 -H (V 4 ), R 4 -O- (G 4 ) 5 -H (V 5 ),
    in the respective molar proportions a'1, a ' 2 , a' 3 , a ' 4 and a' 5 , such that:
    the sum: a'i + a ' 2 + a' 3 + a ' 4 + a' 5 is equal to 1, and the sum a'i + 2a ' 2 + 3a' 3 + 4a ' 4 + 5a' 5 is equal to q; and (η) - From 0% to 12.5% by mass of at least one alcohol of formula (VI):
    R 4 -OH (VI) in which R 4 is as defined for the preceding formula (V).
    By compounds of formula (I) or (II) in acid form, partially or totally salified, it is meant that in the context of the present invention one, more or all of the carboxyl functions present in one or the other of the called compounds of
    2016P00666-EN formula (I) or (II) is either in acid form (-COOH) or in salified form (-COO 'M + ). In the latter case M + represents a monovalent cation chosen from:
    - The ammonium cation,
    - The monovalent cations of alkali metals, for example the cation sodium (Na + ), potassium (K + ) or lithium (Li + ),
    - The (hydroxyalkyl) ammonium, bis (hydroxyalkyl) ammonium or tris (hydroxyalkyl) ammonium cations in which the hydroxyalkyl radical (s) contain from one to four carbon atoms, for example the cations 2-hydroxy ethanammonium, 2-hydroxy propanammonium, bis (2-hydroxy ethyl) ammonium and tris (2-hydroxy ethyl) ammonium,
    - (alkyloxyalkyl) ammonium, bis (alkyloxyalkyl) ammonium or tris (alkyloxyalkyl) ammonium cations in which the alkyloxyalkyl radical (s) contain from two to six carbon atoms, for example the 2-ethoxy ethanammonium cation,
    - The (hydroxyalkylaminoalkyl) ammonium, bis (hydroxyalkylaminoalkyl) ammonium or tris (hydroxyalkylaminoalkyl) ammonium cations, in which the hydroxyalkylaminoalkyl radical (s) contain from two to six carbon atoms, for example the 2-hydroxy ethylaminomethanammonium cation and the 2-hydroxy cation ethylaminoethanammonium.
    By residue of a reducing sugar, the definition of the residues (G 3 ) and (G 4 ) denotes formulas (III) and (V) as defined above, the residues of saccharide derivatives without glycosidic bond established between a carbon. anomeric and oxygen of an acetal group, as they are defined in the reference work: Biochemistry, Daniel Voet / Judith G. Voet, p. 250, John Wyley & Sons, 1990.
    The oligomeric structures (G 3 ) p and (G 4 ) q can be in any form of isomerism, whether it is optical isomerism, geometric isomerism or position isomerism; it can also represent a mixture of isomers.
    In formula (III) as defined above, the group R 3 is linked to G 3 by the anomeric carbon of the saccharide residue, so as to form an acetal function. Similarly, in formula (V) as defined above, the group R 4 is linked to G 4 by the anomeric carbon of the saccharide residue, so as to form an acetal function.
    According to a particular aspect of the mixture (Mi) as defined above, in formula (III) G 3 and G 4 , identical or different, independently of one another, represent the remainder of a reducing sugar, glucose, dextrose , sucrose, fructose, idose,
    2016P00666-EN gulose, galactose, maltose, isomaltose, maltotriose, lactose, cellobiose, mannose, ribose, xylose, arabinose, lyxose, allose, altrose, dextran and tallose.
    By linear or branched, saturated or unsaturated aliphatic radical containing from twelve to sixteen carbon atoms, is denoted in particular for R 3 in formulas (III) and (IV)
    - A linear alkyl radical chosen from the dodecyl (nC 12 H 25 -), tetradecyl (nC 14 H 2 9-) and hexadecyl (nC 16 H 32 -) radicals,
    - A branched alkyl radical derived from iso-alkanols of formula (1):
    (CH 3 ) (CH 3 ) CH- (CH 2 ) r-CH 2 -OH (1) in which r represents an integer between 8 and 16, for example the isododecyl, isotridecyl, isotetradecyl, isopentadecyl or isohexadecyl radical;
    - A branched alkyl radical derived from a Guerbet alcohol of formula (2):
    CH (C s H 2 s + i) (CtH 2 t + i) -CH 2 -OH (2) in which t is an integer between 2 and 12, s is an integer between 2 and 14 and the sum s + t is greater than or equal to 10, and less than or equal to 14, for example the radical 2-ethyl decyl, 2-butyl octyl, 2-ethyl dodecyl, 2-butyl decyl, 2-hexyl octyl, 2-hexyl decyl or 2-butyl dodecyl.
    According to a particular aspect, said surfactant mixture (IVh) is characterized in that in said composition (C 2 ) the proportions of composition (C 4 ) and of alcohol of formula (VI) are zero.
    According to another particular aspect, said surfactant mixture (IVh) is characterized in that in said composition (C 2 ) the proportion of composition (C 4 ) is greater than 0.
    According to another particular aspect, of the present invention, the compounds of formula (I) and of formula (II) are partially or completely salified in the form of sodium salt or potassium salt.
    According to another particular aspect, said mixture (IVh) as defined above comprises for 100% of its mass, from 55% to 99% by mass of said composition (C ^ and from 1% by mass to 45% by mass of said composition (C 2 ), and more particularly from 57% to 99% by mass of said composition (C ^ and from 1% by mass to 43% by mass of said composition (C 2 ).
    According to another particular aspect, the composition (Ci) as defined above comprises for 100% of its mass, from 65% to 90% by mass of one or more compounds of formula (I) and from 10% to 35% by mass one or more
    2016P00666-FR compounds of formula (II); and more particularly from 65% to 85% by mass of one or more compounds of formula (I) and from 15% to 35% by mass of one or more compounds of formula (II).
    In formulas (I) and (II), as defined above, the radical Ri- (C = O) -represent more particularly an acyl radical chosen from the octanoyl, decanoyl, ω-undecylenoyl, dodecanoyl, tetradecanoyl, hexadecanoyl radicals, octadecanoyl, 9-octadecenoyl, 9,12-octadecadienoyl and 9,12,15-octadecatrienoyl.
    The compounds of formulas (I) as described above are generally obtained by N-acylation of the corresponding amino acids or their salts. It is described for example in the international application published under the number WO 98/09611. It is used either on an amino acid or on a mixture of amino acids. The acylating agent generally consists of an activated derivative of the carboxylic acid of formula:
    Ri-C (= O) -OH, in which Ri is as defined above, such as a symmetrical anhydride of this acid, the methyl ester of this acid, or an acid halide such as acid chloride or acid bromide. It can also consist of a mixture of activated derivatives of carboxylic acids obtained from natural oils or fats of animal or vegetable origin such as coconut, coconut, palm kernel, palm, soy, rapeseed oils. , corn, beef tallow, spermaceti oil or herring oil.
    According to another particular aspect, the subject of the invention is said surfactant mixture (Mi) as defined above, characterized in that said composition (Ci) is obtained by a process comprising at least:
    a step A) of acylation of a compound of formula (Vil): NH 2 -CH (COOH) - (CH 2 ) 2 -COOH (Vil),
    In acid form, partially or totally salified, with a mixture of acid chlorides comprising, for 100% molar, from 40% molar to 60% molar dodecanoyl chloride, from 10% molar to 20% molar tetradecanoyl chloride, 5 mol% to 15 mol% of decanoyl chloride, and 5 mol% to 15 mol% of octanoyl chloride, and optionally and up to a maximum of 100 mol%, of hexadecanoyl chloride and / or chloride d octadecanoyl and / or 9octadecenoyl chloride and / or octadeca-9,12-diennoyl chloride.
    2016P00666-FR
    According to a more particular aspect, the mixture of acid chlorides used comprises 100% by mol, 11% by mol of octanoyl chloride, 9.5% by mol of decanoyl chloride, 51% by mol of dodecanoyl chloride, 15, 5 mol% of tetradecanoyl chloride, 6.5 mol% of hexadecanoyl chloride, 2 mol% of octadecanoyl chloride, 3 mol% of 9-octadecenoyl chloride and 1.5% octadeca-9 chloride, 12-diennoyl.
    According to another particular aspect, the subject of the invention is said surfactant mixture (MJ as defined above, characterized in that the compound or compounds of formula (I) are chosen from monosodium N-cocoyl glutamate, monopotassium N-cocoyl glutamate , disodium N-cocoyl glutamate and dipotassium N-cocoyl glutamate.
    According to another particular aspect, the subject of the invention is said surfactant mixture (Mi) as defined above, characterized in that said composition (C 2 ) comprises per 100% of its mass:
    (γ) - A mass proportion in said composition (C 3 ) greater than or equal to 70% and less than 100%, and (δ) - A mass proportion in said alcohol of formula (IV) greater than or equal to 0% and less or equal to 7.5%, (ε) - A mass proportion in said composition (C 4 ) greater than or equal to 0% and less than or equal to 20%, and (η) - A mass proportion in said alcohol of formula ( VI) greater than or equal to 0% and less than or equal to 2.5%.
    According to an even more particular aspect, the subject of the invention is said surfactant mixture (MJ as defined above, characterized in that said composition (C 2 ) as defined above comprises, for 100% of its mass, a mass proportion in said composition (C 3 ) greater than or equal to 90% and less than or equal to 100%, a mass proportion of said alcohol of formula (IV) greater than or equal to 0% and less than or equal to 1.5%, a mass proportion of said composition (C 4 ) equal to 0% to 7% and a mass proportion of said alcohol of formula (VI) equal to 0% to 1.5%.
    According to another particular aspect, the subject of the invention is said surfactant mixture (MJ as defined above, characterized in that in said formula (III), G 3 represents the residue of a reducing sugar chosen from the residues of glucose, xylose and arabinose.
    2016P00666-FR
    According to another particular aspect, the subject of the invention is said surfactant mixture (Mi) as defined above, characterized in that in said formula (III), p represents a decimal number greater than or equal to 1.05 and less than or equal to 2.5, more particularly greater than or equal to 1.05 and less than or equal to 2.0, and even more particularly greater than or equal to 1.25 and less than or equal to 2.0.
    According to another particular aspect, the subject of the invention is said surfactant mixture (Mi) as defined above, characterized in that the formulas (III) and (IV), the radical R 3 represents a linear alkyl radical chosen from the radicals dodecyl (n-C12H25-), tetradecyl (n-Ci 4 H 2 9-) and n-hexadecyl (n-Ci 6 H 32 -).
    According to another particular aspect, the invention relates to said surfactant mixture (Mi) as defined above, characterized in that in formula (V), G 4 represents the remainder of a reducing sugar chosen from the remains of glucose , xylose and arabinose.
    According to another particular aspect, the subject of the invention is said surfactant mixture (Mi) as defined above, characterized in that in formula (V), q represents a decimal number greater than or equal to 1.05 and less than or equal 2.5, more particularly greater than or equal to 1.05 and less than or equal to 2.0, and even more particularly greater than or equal to 1.25 and less than or equal to 2.0.
    According to a particular aspect, the subject of the invention is said surfactant mixture (Mi) as defined above, characterized in that in the formulas (V) and (VI), R 4 represents a linear alkyl radical chosen from the hexyl radicals (nC 6 Hi 3 -), heptyle (nC 7 H 15 -) and (2-ethyl hexyl).
    According to an even more particular aspect, in formulas (V) and (VI), R 4 represents the heptyl radical (nC 7 Hi 5 -).
    According to another even more particular aspect, in formulas (V) and (VI), R 4 represents the n-hexyl radical (nC 6 Hi 3 -).
    According to another even more particular aspect, in formulas (V) and (VI), R 4 represents the radical the 2-ethyl-hexyl radical.
    According to another particular aspect, the surfactant mixture (Μ Ί ) as defined above, characterized in that said composition (C 2 ) comprises a mixture of compositions (C 3 ) and of compositions (C 4 ), said mixture comprising for 100 % of its mass:
    2016P00666-FR (γι) - From 30% to 90% by mass, more particularly from 50% to 89% by mass of a composition (C 3 ) represented by formula (III) in which R 3 represents the dodecyl radical (n- Ci 2 H 25 -), (γ 2 ) - From 9% to 40% by mass, more particularly from 10% to 30% by mass of a composition (C 3 ) represented by formula (III) in which R 3 represents the tetradecyl radical (nC 14 H 29 -), and (γ 3 ) - - From 1% to 10% by mass, more particularly from 1% to 5% by mass of a composition (C 3 ) represented by formula (III) in which R 3 represents the hexadecyl radical (nC 16 H 32 -), and (êi) - From 0% to 20% by mass, more particularly from 0% by mass to 15% by mass, of a composition (C 4 ) represented by the formula (V) in which R 4 represents the heptyl radical (nC 7 H 15 -).
    According to another particular aspect, the surfactant mixture (Mi) as defined above, characterized in that said composition (C 2 ) comprises a mixture of compositions (C 3 ) and of compositions (C 4 ), said mixture comprising for 100% its mass: - From 30% to 90% by mass, more particularly from 35% to 89% by mass, and even more particularly from 50% to 89% by mass, of a composition (C 3 ) represented by the formula (III) in which R 3 represents the dodecyl radical (n-Ci 2 H 25 -),
    - From 9% to 40% by mass, more particularly from 10% to 40% by mass, and even more particularly from 10% to 30% by mass, of a composition (C 3 ) represented by the formula (III) in which R 3 represents the tetradecyl radical (nC 14 H 29 -), and
    - From 1% to 10% by mass, more particularly from 1% to 5% by mass, and even more particularly from 1% to 5% by mass, of a composition (C 3 ) represented by the formula (III) in which R 3 represents the hexadecyl radical (nC 16 H 32 -), and
    - from 0% to 20% by mass, more particularly from 0% to 20% by mass, and even more particularly from 0% by mass to 15% by mass, of a composition (C 4 ) represented by the formula (V) in which R 4 represents the radical the 2-ethyl hexyl radical.
    According to another particular aspect, the surfactant mixture (M ^ as defined above, characterized in that the composition (C 2 ) comprises a mixture of compositions (C 3 ) comprising for 100% of its mass:
    2016P00666-FR
    - From 50% to 90% by mass, more particularly from 70% to 90% by mass, and even more particularly from 80% to 90% by mass, of a composition (C 3 ) represented by the formula (III) in which R 3 represents the dodecyl radical (nC 12 H 25 -),
    - From 9% to 40% by mass, more particularly from 9% to 25% by mass, and even more particularly from 9% to 15% by mass, of a composition (C 3 ) represented by the formula (III) in which R 3 represents the tetradecyl radical (nC 14 H 29 -), and
    - From 1% to 10% by mass, more particularly from 1% to 5% by mass, and even more particularly from 1% to 5% by mass, of a composition (C 3 ) represented by the formula (III) in which R 3 represents the n-hexadecyl radical (nC 16 H 32 -).
    According to a more particular aspect, the surfactant mixture (Mi) as defined above, characterized in that in formula (III), G 3 represents the residue of a reducing sugar chosen from the residues of glucose, xylose and l 'arabinose, p represents a decimal number greater than or equal to 1.05 and less than or equal to 2.5, more particularly greater than or equal to 1.05 and less than or equal to 2.0, and even more particularly greater than or equal to 1.25 and less than or equal to 2.0, and R 3 represents a linear alkyl radical chosen from the dodecyl (nC 12 H 25 -), tetradecyl (nC 14 H 29 -), and hexadecyl (nC 16 H 32 -) radicals ).
    According to an even more particular aspect, the surfactant mixture (MQ as defined above, is characterized in that in formula (III), G 3 represents the remainder of the glucose, p represents a decimal number greater than or equal to 1.05 and less than or equal to
    2,5, and R 3 represents a linear alkyl radical chosen from the dodecyl (n-Ci 2 H 25 -), tetradecyl (nC 14 H 29 -), and hexadecyl (nC 16 H 32 -) radicals.
    According to another more particular aspect, the surfactant mixture (Mi) as defined above, is characterized in that in formula (III) G 3 represents the rest of the xylose, p represents a decimal number greater than or equal to 1.05 and less than or equal to
    2.5, and R 3 represents a linear alkyl radical chosen from the dodecyl radicals (n-Ci 2 H 25 -), the tetradecyl radical (nC 14 H 29 -), and the hexadecyl radical (nC 16 H 32 -).
    According to another more particular aspect, the surfactant mixture (M ^ as defined above, is characterized in that in formula (V), G 4 represents the residue of a reducing sugar chosen from the residues of glucose, xylose and arabinose, q represents a decimal number greater than or equal to 1.05 and less than or equal to 2.5, more particularly greater than or equal to 1.05 and less than or equal to 2.0, and even more particularly greater or equal to 1.25 and less than or equal to 2.0, and R 4 represents a
    2016P00666-FR aliphatic alkyl radical chosen from hexyl radicals (nC 6 H 13 -), heptyl radical (nC 7 H 15 -) and (2-ethyl hexyl).
    According to an even more particular aspect, the surfactant mixture (Μ () as defined above, is characterized in that in the formula (V), G 4 represents the remainder of the glucose, q represents a decimal number greater than or equal to 1, 05 and less than or equal to
    2.5, and R 4 represents an aliphatic alkyl radical chosen from the hexyl (nC 6 H 13 -), heptyl (nC 7 H 15 -) and (2-ethyl-hexyl) radicals.
    According to an even more particular aspect, the surfactant mixture (IVh) as defined above, is characterized in that in the formula (V), G 4 represents the remainder of the glucose, q represents a decimal number greater than or equal to 1.05 and less than or equal to
    2.5, and R 4 represents the heptyl radical (nC 7 H 15 -).
    According to another even more particular aspect, the surfactant mixture (Mi) as defined above, is characterized in that in formula (V), G 4 represents the rest of the xylose, q represents a decimal number greater than or equal to 1, 05 and less than or equal to 2.5, and R 4 represents an aliphatic alkyl radical chosen from the hexyl (nC 6 H 13 -), heptyl (nC 7 H 15 -) and (2-ethyl-hexyl) radicals.
    According to a very particular aspect, the surfactant mixture (Μ Ί ) as defined above, is characterized in that in the formula (V), G 4 represents the rest of the xylose, q represents a decimal number greater than or equal to 1.05 and less than or equal to
    2.5, and R 4 represents the heptyl radical (nC 7 H 15 -).
    According to an even more particular aspect, the surfactant mixture (Μ Ί ) as defined above, is characterized in that the composition (C 3 ), is obtained by the implementation of a process comprising at least one step A ') glycosylation of:
    - One to five molar equivalents, more particularly two to four molar equivalents, even more particularly three to four molar equivalents, of a mixture of alcohols comprising for 100% molar:
    - from 40% to 90% molar of dodecanol-1, more particularly from 65% to 90% molar, and even more particularly from 75% to 90% molar,
    - from 9% to 40% molar of tetradecanol-1, more particularly from 9% to 20% molar, and even more particularly from 9% to 20% molar, and
    - from 1 mol% to 20 mol% of hexadecanol-1, more particularly from 1% to 15 mol%, and even more particularly from 1% to 5 mol%,
    - With a molar equivalent of a reducing sugar of formula (VII):
    2016P00666-FR
    HO- (G 3 ) -H (VII) in which G 3 represents the residue of a reducing sugar chosen from the residues of glucose, xylose and arabinose.
    According to another particular aspect, the surfactant mixture (Mi) as defined above, is characterized in that the composition (C 4 ), is obtained by the implementation of a process comprising at least one step A / of glycosylation of :
    - One to four molar equivalents, more particularly from one to three molar equivalents, even more particularly from two to three molar equivalents of at least one alcohol of formula (VI), with a molar equivalent of a reducing sugar of formula (VIII) ):
    HO- (G 4 ) -H (VIII) in which G 4 represents the remainder of a reducing sugar chosen from the remains of glucose, xylose and arabinose.
    According to another particular aspect, the surfactant mixture (Mi) as defined above, is characterized in that the composition (C 3 ) is obtained by the implementation of a process comprising at least one step A 'of glycosylation generally carried out with mechanical stirring, by bringing one molar equivalent of a reducing sugar (G 3 ) into contact with one to five molar equivalents of the mixture of dodecanol-1, tetradecanol-1, and hexadecanol-1, as described above, in the presence of an acidic catalytic system, under predetermined temperature and partial vacuum conditions.
    Likewise, step N ′ of the process for preparing the composition (C 4 ), as defined above, is generally carried out with mechanical stirring, by bringing a molar equivalent of a reducing sugar (G 4) into contact. ) with from one to four molar equivalents of at least one alcohol of formula (V), in the presence of an acidic catalytic system, under predetermined temperature and partial vacuum conditions.
    Such conditions of temperature and partial vacuum are, for example, temperature values between 70 ° C and 130 ° C, and a partial vacuum between 300 mbar (3.10 4 Pa) and 20 mbar (2.10 3 Pa). Carrying out step A ′ and step A / of glycosylation makes it possible to respectively form the composition (C 3 ), ie a mixture of compounds represented by the formulas (llh), (lll 2 ), (III3), (III 4 ) and (III5) as defined above, and optionally an excess of the alcohol of formula (IV) or of the mixture of alcohols of formula (IV), and the composition (C 4 ), ie a mixture of compounds
    2016P00666-FR represented by the formulas (VJ, (V 2 ), (V 3 ), (V 4 ) and (V 5 ) as defined above, and optionally an excess of the alcohol of formula (VI).
    If necessary or if desired, step A 'or step AJ of the process for the preparation of the respective compositions (C 3 ) and (C 4 ) as defined above, can be followed respectively by step B' or d ' a step BJ of elimination of the alcohols of formula (IV) respectively, or of the mixture of alcohols of formula (IV), and of formula (VI), which have not reacted during step A ') or the AJ stage.
    Such a preparation process can be supplemented, if necessary or if desired, by neutralization, filtration and discoloration operations.
    The expression “acid catalytic system” denotes, in step A 'and in step AJ of the process defined above, strong acids such as sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid. , methane sulfonic acid, (para-toluene) sulfonic acid, (trifluoromethane) sulfonic acid, hypophosphorous acid, hyponitrous acid, polyphosphoric acid, or ion exchange resins.
    During step B ') or step ΒΊ) of the process as described above, the alcohols of formula (IV) respectively, or the mixture of alcohols of formula (IV), or the alcohol of formula (V) are eliminated according to methods known to a person skilled in the art such as, for example, by distillation, such as hard film thin film distillation, molecular distillation or extraction by solvents.
    According to a particular aspect, the surfactant mixture (MJ as defined above) is characterized in that, the mass ratio
    Δ = Mass of compound (s) of formula (I) / [Mass of the composition (C 3 )] + Mass of the composition (C 4 )], is greater than or equal to 65/35 and less than or equal to 90 / 10, more particularly greater than or equal to 70/30 and less than or equal to 90/10 even more particularly greater than or equal to 75/25 and less than or equal to 85/15.
    The subject of the invention is also a composition (C A ) characterized in that it comprises for 100% by mass:
    a) - From 5% to 85% by mass, more particularly from 20% to 60% by mass and even more particularly from 30% to 50% by mass of said (MJ as defined above, and
    b) - From 15% to 95% by mass, more particularly from 40% to 80% by mass, and even more particularly from 50% to 70% by mass of water.
    The invention further relates to a composition (C E ) characterized in that it comprises for 100% by mass:
    2016P00666-FR
    a) - From 0.1% to 25% by mass, more particularly from 0.15% to 25% by mass, and even more particularly from 0.2% to 25% by mass of said mixture (Mi) as defined above;
    b) - From 55% to 99.75% of water, more particularly from 58.5% to 99.7% by mass, and even more particularly from 61% to 99, 65% by mass of water;
    c) - From 0.05% to 10% by mass, more particularly from 0.05% to 7.5% by mass and even more particularly from 0.05% to 6% by mass of at least one fluorinated surfactant (ATF) chosen from anionic fluorinated surfactants, cationic surfactants, nonionic surfactants and amphoteric surfactants,
    d) - From 0.1% to 10% by mass, more particularly from 0.1% to 9% by mass and even more particularly from 0.1% to 8% by mass of at least one gelling and / or thickening agent (AG ) chosen from polysaccharides consisting of derivatives of oses, polysaccharides consisting only of oses, cellulose and cellulose derivatives, starches and polyelectrolytes which are linear or branched or crosslinked.
    By fluorinated surfactants is meant in the definition of the composition (C E ) as defined above, the organo-fluorinated amphiphilic compounds containing several fluorine atoms, which can be of polyfluorinated or perfluorinated nature.
    The term “perfluorinated surfactant” denotes a compound containing a hydrophilic radical and a terminal aliphatic perfluorocarbon radical of at least three carbon atoms and in particular a perfluorinated radical of formula (3):
    CF 3 - (CF 2 ) m - (3), in which m represents an integer between 2 and 11.
    The branched perfluorocarbon radical of formula (3) is generally chosen from those represented by the following formulas (3.1), (3.2), (3.3), (3.4), (3.5) and (3.6):
    (CF 3 ) 2 CF (CF 2 ) m - (3.1), in which m 'represents an integer between 2 and 11;
    CF 3 -CF 2 -C (CF 3 ) = C (CF 2 -CF 3 ) -CF 2 - (3.2), [(C 2 F 5 ) 2 ] C (CF 3 ) -C (CF 3 ) = C (CF 3 ) - (3.3),
    CF 3 -CF 2 -C (CF 3 ) = C (CF 3 ) -CF 2 -CF 2 - (3.4), (C 2 F 5 ) 2 C (CF 3 ) -CH 2 - (3.5), (C 2 F 5 ) 2 C (CF 3 ) -CH = C (CF 3 ) - (3.6).
    2016P00666-FR
    According to another particular aspect, the subject of the invention is a composition (C E ) characterized in that it comprises one or more anionic fluorinated surfactants chosen from the compounds of formulas (4), (4.1), (4.2) and (4.3) following:
    RfSO 3 'X + (4),
    R f (CH 2 ) s -COO'X + (4.1),
    RrO-C 6 H 4 -SO 3 'X + (4.2),
    R r O- C 6 H 4 -CH 2 -PO 4 'X + (4.3), in which:
    - R f represents a radical of the following formulas (4 ') or (4 ”):
    C r F 2r -i (4 ')
    C r F 2r + 1 (4 ”), in which r is an integer greater than or equal to 4 and less than or equal to 12,
    - X + represents a proton or a monovalent cation chosen from:
    - The ammonium cation,
    - The monovalent cations of alkali metals, for example the cation sodium (Na + ), potassium (K + ) or lithium (Li + ),
    - The (hydroxyalkyl) ammonium, bis (hydroxyalkyl) ammonium or tris (hydroxyalkyl) ammonium cations in which the hydroxyalkyl radical (s) contain from one to four carbon atoms, for example the cations 2-hydroxy ethanammonium, 2-hydroxy propanammonium, bis (2-hydroxy ethyl) ammonium and tris (2-hydroxy ethyl) ammonium,
    - (alkyloxyalkyl) ammonium, bis (alkyloxyalkyl) ammonium or tris (alkyloxyalkyl) ammonium cations in which the alkyloxyalkyl radical (s) contain from two to six carbon atoms, for example the 2-ethoxy ethanammonium cation,
    - The cations (hydroxyalkylaminoalkyl) ammonium, bis (hydroxyalkylamino alkyl) ammonium or tris (hydroxyalkylaminoalkyl) ammonium, in which the hydroxyalkylaminoalkyl radical (s) contain from two to six carbon atoms, for example the 2-hydroxy ethylaminomethanammonium cation and the cation 2- hydroxy ethylaminoethanammonium, and
    - s represents an integer greater than or equal to 0 and less than or equal to 6.
    2016P00666-FR
    According to another particular aspect, the subject of the invention is a composition (C E ) characterized in that it comprises one or more cationic fluorinated surfactants are chosen from those of formulas (4.4), (4.5), and (4.6) following:
    RrSO 2 -N (R) - (CH 2 ) sN + (R) 3 Y (4.4),
    RrO-C 6 H 4 -CH 2 -N + (R) 3 Y '(4.5),
    R r C 6 H4-SO 2 -N (R) - (CH 2 ) sN + (R) 3 Y (4.6), in which:
    - R f represents a radical represented by the formula (4 ') or by the formula (4 ”) as described above,
    - s represents an integer greater than or equal to 0 and less than or equal to 6 as described above,
    Y 'represents a monovalent anion chosen from chloride, bromide, iodide, and methosulfate anions,
    - R represents the hydrogen atom or an alkyl radical, linear or branched, containing from one to four carbon atoms.
    According to another particular aspect, the subject of the invention is a composition (C E ) characterized in that it comprises one or more nonionic fluorinated surfactants of formulas (4.7), (4.8), (4.9), (4.10) and (4.11) following:
    R r O- (CH 2 CH 2 O) t -R (4.7),
    R r O- (CH 2 CH 2 O) t -R f (4.8),
    RrO-C 6 H 4 -CH 2 -O- (CH 2 CH 2 O) tR (4.9),
    R r OC 6 H4-CH 2 -O- (CH 2 CH 2 O) tR f (4.10), RrO-C6H4-SO 2 -O- (CH 2 CH 2 O) t-SO 2 -C6H4-OR f ( 4.11) in which:
    - R f represents a radical represented by the formula (4 ') or by the formula (4 ”) as described above,
    - R represents the hydrogen atom or an alkyl radical, linear or branched, comprising from one to four carbon atoms,
    -1 represents an integer greater than or equal to 1 and less than or equal to 40.
    According to another particular aspect, the invention relates to a composition (C E ) characterized in that it comprises one or more fluorinated amphoteric surfactants chosen from
    2016P00666-FR
    - Those of formulas (4.12), (4.13), (4.14), (4.15), (4.16), (4.17) and (4.18) following:
    R f (CH 2 ) s -SO2-N (R 5 ) - (CH 2 ) s -N + (R 6 ) (R7) - (CH 2 ) u -COO · (4.12)
    Rf (CH 2 ) s-SO2-N (R5) - (CH 2 ) sN + (R6) (R7) - (CH 2 ) <SO3 · (4.13)
    Rf (CH 2 ) w -S-CH 2 CH (OH) -CH2-N + (R 6 ) (R7) - (CH 2 ) u -COO · (4.14)
    R f (CH 2 ) w -S-CH 2 CH (OH) -CH2-N + (R6) (R7) - (CH 2 ) v -SO 3 (4.15)
    Rf (CH 2 ) w -S-CH (COO ') - CH 2 CONH (CH2) s'-N + H (R 6 ) (R7) (4.16)
    R f (CH 2 ) s -SO2-N (R 8 ) - (CH2) s'-N (R 6 ) (R7HO (4.17)
    R f (CH 2 ) w -S-CH2-CH (OH) -CH 2 -N + (R 6 ) (R7) (R9), CI '(4.18) in which:
    - R f represents a radical represented by the formula (4 ') or by the formula (4 ”) as described above,
    - R5 represents the hydrogen atom or an alkyl radical, linear or branched, comprising from one to four carbon atoms,
    - s ’and u, identical or different, represent an integer greater than or equal to 1 and less than or equal to 5,
    - v represents an integer equal to 2 or 3,
    - R 6 , R 7 , R g , identical or different, each represent a methyl or ethyl radical,
    - w represents an integer greater than or equal to 1 and less than or equal to 6;
    - Those of formulas (4.19), (4.20), (4.21), (4.22) and (4.23) following:
    C r F 2r + i-CH 2 -CH2-SO2-NH-CH2-CH2-N + (CH 3 ) 2-COO ((4.19),
    CrF2r + i-CH 2 -CH2-S-CH2-CH (OH) -CH2-N + (CH 3 ) 2-CH2-COO (4.20),
    CrF2r + i-CH 2 -CH2-SO2-N (CH3) - (CH2) 3-N + (CH 3 ) 2-CH2-CH 2 -CH2-COO · (4.21),
    Cr'F2r ' + i-CH 2 -CH2-SO2-NH- (CH2) 3-N (CH 3 ) 2 ^ O (4.22),
    CrF2r + i-CH 2 -CH2-S-CH (COO ') CH2CONH (CH2) 3-N + H (CH 3 ) 2 (4.23), in which r' is an even integer greater than or equal to 4 and less or equal to 20, and it is more particularly even greater than or equal to 6 and less than or equal to 20;
    (4.24) (4.25) (4.26)
    - Those of formulas (4.24), (4.25), (4.26), (4.27), (4.28), (4.29), (4.30), (4.31) and (4.32) following:
    C6Fi3-CH 2 -CH2-SO2-NH-CH2-CH2-N + (CH 3 ) 2-COO
    C6Fi3-CH 2 -CH2-SO2-NH-CH2-CH2-CH2-N + (CH 3 ) 2-CH2 - COO
    C8Fi7-SO2-NH-CH2-CH2-CH2-N + (CH 3 ) 2-CH 2 -COO
    2016P00666-FR
    C6Fi3-CH2-CH2-SO2-NH-CH2-CH2-CH2-N + (CH 3 ) 2-CH2-CH2-COO (4.27)
    C6F13-CH2-CH2-SO2-NH-CH2-CH2-CH2-N + (CH 3 ) 2-CH2-CH2-CH2-COO (4.28)
    C6Fi3-CH2-CH2-SO2-N (CH3) -CH2-CH2-CH2-N + (CH 3 ) 2-CH2-CH2-CH2-COO '(4.29)
    C 6 Fi3-CH2-CH2-S-CH2-CH (OH) -CH2-N + (CH3) 2-CH2-COO (4.30)
    C 6 F13-CH2-CH2-SO2-NH- (CH 2 ) 3-N (CH 0 ) 2 ^ O (4.31)
    C 6 Fi3-CH2-CH2-SO2-N (CH3) - (CH2) 3-N (CR 3 ) 2 ~ ^ O (4.32)
    In the context of the present invention, by thickening agent, is meant a chemical compound or a chemical composition which increases the viscosity of the medium into which it is introduced. In the context of the present invention, by gelling agent, is meant a chemical compound or a chemical composition which transforms a liquid medium into a structured state, which does not flow, by forming a three-dimensional network within the liquid; the gel being considered as an intermediate state between the liquid state and the solid state.
    In the context of the present invention, the term “polysaccharides” denotes polymers of saccharides. The IUPAC definition of saccharides designates oses, compounds of oses proper and their derivatives obtained either by reduction of a carbonyl group, or by oxidation of one or more hydroxyl functions, or by replacement of one or more functions hydroxyls by a hydrogen atom, by an amine group, a phosphate function, a sulfate function. The polysaccharides most commonly used for the preparation of industrial, food, cosmetic or pharmaceutical compositions, are mainly made up of oses, such as glucose, galactose, mannose or derivatives of oses for which the hydroxyl function of the terminal carbon has been oxidized to a carboxyl function. Two distinct groups can be distinguished among polysaccharides: polysaccharides consisting only of oses (or poly-oses) and polysaccharides consisting of derivatives of oses.
    According to a particular aspect, the gelling agents and / or thickeners present in the aqueous composition (C E ) which is the subject of the present invention are chosen from polysaccharides consisting solely of oses (or poly-oses).
    Among the polysaccharides composed entirely of oses, one can distinguish glucans, which are homopolymers of glucose abundant in nature, glucomannoglycans, xyloglycans and galactomannans, which are polymers
    2016P00666-FR whose main chain consists of D-mannose units, linked together in β-1,4, and on which D-galactose units are grafted laterally by a-1,6 bonds. Galactomannans are present in several plant species, and more particularly in legume species in which they constitute the albumen of seeds. Depending on their plant origin, the degree of substitution (DS) of D-galactose units on the main D-mannose chain of galactomannans, varies between 0 and 1: galactomannans from cassia gum have a degree of substitution (DS ) of about 1/5, meaning the lateral grafting of a unit of D-galactose every 5 units of D-mannose present on the main chain of polysaccharide I - The galactomannans from locust bean gum have a degree of substitution (DS) of approximately 1/4, signifying the lateral grafting of one unit of D-galactose every 4 units of D-mannose present on the main chain of the polysaccharide
    - The galactomannans from tara gum have a degree of substitution (DS) of about 1/3, meaning the lateral grafting of one unit of D-galactose every 3 units of D-mannose present on the main chain of polysaccharide
    - The galactomannans from guar gum have a degree of substitution (DS) of approximately 1/2, signifying the lateral grafting of a unit of D-galactose every 2 units of D-mannose present on the main chain of polysaccharide
    - The galactomannans from fenugreek gum have a degree of substitution (DS) of about 1/1, meaning the lateral grafting of a D-galactose unit for almost all the D-mannose units present on the main chain polysaccharide.
    According to a more particular aspect, the gelling agents and / or thickeners present in the aqueous composition (C E ) which is the subject of the present invention are chosen from the polysaccharides consisting solely of oses (or poly-oses) included in the group consisting of galactomannan from Tara gum, galactomannan from guar gum and galactomannan from carob gum.
    According to another particular aspect, the gelling agents and / or thickeners present in the aqueous composition (C E ) which is the subject of the present invention are chosen from polysaccharides consisting of derivatives of oses. Among the polysaccharides made up of derivatives of oses, one can distinguish:
    2016P00666-FR
    - Sulphated galactans, which are galactose polymers which can have appendix sulphate ester groups, represented in particular by algal polysaccharides such as carrageenans and agar;
    - Uronanes, which are polymers of uronic acids such as algin and pectin;
    - The heteropolymers of oses and uronic acids: often of complex composition, these polymers are found in particular in the exudates of sap (such as for example the exudate of gum arabic and the exudate of karaya gum) but they are also produced by microorganisms, such as, for example, xanthan gum and gellan gum;
    - Glucosaminoglycans which are polysaccharides formed from glucose derived by replacing its hydroxyl on C-2 with an amine (called 2-amino-2-deoxy-D-glucose or, more simply, glucosamine). The amine function can also be acetylated. Among the hydrocolloids in this class are chitosan, formed only of glucosamine units, and hyaluronan, the repeat unit of which is a dimer of glucosamine and glucuronic acid.
    Xanthan gum (G x ) has become in recent decades the most used microbial polysaccharide in the industry. Xanthan is a polysaccharide synthesized by bacteria of the genus Xanthomonas and, commercially, only the species X. campestris is used. The main chain of (G x ) is identical to that of cellulose, that is to say that it is formed of β-D-glucose units linked by carbons 1 and 4. There is a branched triholoside every two units of glucose in the main chain, alternately regularly; each branch consisting of a triholoside composed of two mannoses and a glucuronic acid, of the type: β-D-Manp-fl -> 4) -pD-GlcAp- (1 -> 2) -a-DManp- (1 - > 3) [I. Capron and a. “About the native and renaturated conformation ofxanthan exopolysaccharide”. 1997). Xanthan gum (GX) is available as a sodium, potassium or calcium salt.
    Acacia gum is a branched complex polysaccharide whose main chain consists of β-D-galactose units linked together by carbons 1 and 3. The chains connected to the main chain are made up of β-D units -galactose linked together by carbons 1 and 6, also carrying α-arabinose units, and in lesser proportions β-glucoronosyl units. Both the chain
    2016P00666-FR main and pendant chains contain α-L-arabinosyle, a-L-rhamnopyranosyle, β-D-glucuronopyranosyle and 4-O-methyl-p-D-glucuronopyranosyle units.
    According to a more particular aspect, the gelling agents and / or thickeners present in the aqueous composition (C E ) object of the present invention are polysaccharides consisting of derivatives of oses chosen from the elements of the group consisting of carrageenans, agar , algin, pectin, gum arabic exudate, karaya gum exudate, xanthan gum, gellan gum, chitosan and hyaluronan, and / or mixtures thereof.
    According to an even more particular aspect, the gelling agents and / or thickeners present in the aqueous composition (C E ) which is the subject of the present invention are polysaccharides consisting of derivatives of oses selected from the group consisting of the exudate of the gum arabic, karaya gum exudate, xanthan gum and / or mixtures thereof.
    According to an even more particular aspect, the gelling agents and / or thickeners present in the aqueous composition (C E ) which is the subject of the present invention are polysaccharides consisting of derivatives of oses selected from the group consisting of the exudate of the gum arabic, xanthan gum, the mixture of xanthan gum (G x ) and gum arabic exudate (G A ) used in a mass ratio between xanthan gum (G x ) and exudate gum acacia (G A ) is greater than or equal to 1/3 and less than or equal to 3/1, in particular marketed by SEPPIC under the brand name SOLAGUM ™ AX.
    According to a particular aspect, the gelling agents and / or thickeners present in the aqueous composition (C E ) which is the subject of the present invention are chosen from cellulose and cellulose derivatives.
    In the context of the present invention, “cellulose” denotes a polysaccharide which is constituted by a linear chain of D-Glucose molecules, the average molecular mass of which is at least 10,000 gmol · 1 , more particularly at least minus 15,000gmol ' 1 , more particularly at least 17,000gmol · 1 , even more particularly at least 20,000gmol · 1 , even more particularly at least 25,000gmol · 1 .
    According to a more particular aspect, the gelling agents and / or thickeners present in the aqueous composition (C E ) which is the subject of the present invention are chosen from
    2016P00666-FR
    In the context of the present invention, “cellulose derivatives” denotes the elements of the group consisting of hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, methyl hydroxy ethyl cellulose, methyl hydroxy propyl cellulose, Hydroxy propyl cellulose, the sodium salt of carboxy methyl cellulose, dihydroxy propyl cellulose ether (as described in the American patent published under the number US 4,096,326).
    In the context of the present invention, by “starch” denotes a mixture of amylose and amylopectin, and more particularly the elements of the group consisting of corn starch, wheat starch, potato starch and cassava starch.
    According to a particular aspect, by “polymers of polyelectrolyte type, linear or branched or crosslinked”, is meant within the meaning of the present invention:
    - crosslinked synthetic anionic copolymers based on methacrylic acid or acrylic acid, or esters of methacrylic acid or acrylic acid, optionally hydrophically modified, prepared by direct emulsion polymerization. These synthetic anionic copolymers are respectively known to a person skilled in the art under the names Alkaline Swellable Emulsion (or ASE) and Hydrophobically Alkaline Swellable Emulsion (or HASE). HASE type thickening agents are described in the international application published under the number WO 02/34793 A2;
    - Synthetic anionic polyelectrolytes, crosslinked or branched, which are crosslinked and / or branched homopolymers or copolymers of water-soluble unsaturated monomers, such as acrylic acid and / or its derivatives, methacrylic acid and / or its derivatives, acrylamide and / or its derivatives, 2-acrylamido-2-methylpropanesulfonic acid and / or its salts, N-vinyl pyrrolidone, vinyl alcohol and / or its derivatives. These synthetic anionic polyelectrolytes, crosslinked or branched, are in the form of reverse latexes, obtained by radical polymerization in reverse emulsion, or in the form of powders, obtained by precipitating polymerization or by atomization of reverse latexes.
    According to a particular aspect, the gelling agents and / or thickeners present in the aqueous composition (C E ) which is the subject of the present invention are chosen from linear or branched or crosslinked polyelectrolytes, originating from the radical polymerization of at least one selected monomer among the elements of the group consisting of acrylic acid and / or its sodium salt, methacrylic acid and / or its sodium salt,
    2016P00666-FR 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, acrylamide, Ν, Ν-dimethyl acrylamide, N-isopropyl acrylamide, 2-acrylamido-2-methylpropanesulfonic acid and / or its sodium or potassium salt, N-vinyl pyrrolidone, in the presence of a crosslinking agent chosen from polyethylene monomers comprising at least two ethylenic functions, and more particularly chosen from the elements of the group consisting of dimethacrylate d ethylene glycol, tetraallyloxyethane, ethylene glycol diacrylate, diallyl urea, triallyl amine, trimethylol propanetriacrylate or methylene-bis (acrylamide) or a mixture of these compounds.
    According to a particular aspect, the gelling agents and / or thickeners present in the aqueous composition (C E ) object of the present invention are chosen from the elements of the group consisting of:
    - The homopolymer of partially or fully salified acrylic acid, crosslinked with triallyl amine and / or trimethylol propanetriacrylate and / or methylene-bis (acrylamide),
    - The homopolymer of the sodium salt of 2-acrylamido 2-methyl propanesulfonic acid, crosslinked with triallyl amine and / or trimethylol propanetriacrylate and / or methylene-bis (acrylamide),
    - The copolymer of the sodium salt of 2-acrylamido 2-methyl propanesulfonic acid and partially or fully salified acrylic acid, crosslinked with triallyl amine and / or trimethylol propanetriacrylate and / or methylene-bis (acrylamide),
    - The copolymer of the sodium salt of 2-acrylamido 2-methyl propanesulfonic acid and 2-hydroxy ethyl acrylate, crosslinked with triallyl amine and / or trimethylol propanetriacrylate and / or methylene-bis (acrylamide),
    - The copolymer of the sodium salt of 2-acrylamido-2-methyl propanesulfonic acid and of acrylamide, crosslinked with triallyl amine and / or with trimethylol propanetriacrylate and / or with methylene-bis (acrylamide),
    - The terpolymer of the sodium salt of 2-acrylamido 2-methyl propanesulfonic acid, of acrylamide and partially or fully salified acrylic acid, crosslinked with triallyl amine and / or trimethylol propanetriacrylate and / or methylene-bis (acrylamide),
    - The terpolymer of the sodium salt of 2-acrylamido 2-methyl propanesulfonic acid, of Ν, Ν-dimethylacrylamide, and partially or acrylic acid
    2016P00666-FR fully salified, crosslinked with triallyl amine and / or trimethylol propanetriacrylate and / or methylene-bis (acrylamide).
    According to a more particular aspect, the gelling agents and / or thickeners present in the aqueous composition (C E ) which is the subject of the present invention are chosen from the elements of the group consisting of xanthan gum, exudate of gum acacia, the mixture of xanthan gum (G x ) and arabic gum exudate (G A ) in a mass ratio between xanthan gum (G x ) and acacia exudate gum (G A ) is greater than or equal to 1/3 and less than or equal to 3/1, the copolymer of the sodium salt of 2-acrylamido 2-methyl propanesulfonic acid and 2-hydroxy ethyl acrylate, crosslinked with triallyl amine and / or trimethylol propanetriacrylate and / or methylene bis (acrylamide), the sodium salt copolymer of 2-acrylamido-2-methyl propanesulfonic acid and acrylamide, crosslinked with triallyl amine and / or trimethylol propanetriacrylate and / or methylene-bis (acrylamide).
    According to another particular aspect, the subject of the invention is the aqueous composition (C E ) as defined above, characterized in that it comprises for 100% of its mass:
    a) - From 0.1% to 25% by mass, more particularly from 0.15% to 25% by mass, and even more particularly from 0.2% to 25% by mass of said mixture (Mi) in which:
    - The compound of formula (I) is chosen from monosodium N-cocoyl glutamate, monopotassium N-cocoyl glutamate, disodium N-cocoyl glutamate, dipotassium N-cocoyl glutamate,
    - The compound of formula (II) is chosen from sodium cocoate and potassium cocoate,
    - In formula (III), R 3 represents a linear or branched, saturated or unsaturated aliphatic radical, comprising from 12 to 16 carbon atoms, G 3 represents the remainder of glucose or xylose and p represents a decimal number greater than or equal 1.05 and less than or equal to 2.5;
    - In formula (IV), R 3 represents a linear or branched, saturated or unsaturated aliphatic radical, comprising from 12 to 16 carbon atoms,
    - In formula (V), R 4 represents an aliphatic radical, chosen from the n-heptyl and 2-ethyl hexyl radicals, G 4 represents the remainder of glucose or xylose and q represents a decimal number greater than or equal to 1, 05 and less than or equal to 2,
    2016P00666-FR
    - In formula (VI), R 4 represents an aliphatic radical, chosen from the n-heptyl and 2-ethyl hexyl radicals.
    b) - From 55% to 99.75%, more particularly from 58.5% to 99.7% by mass, and even more particularly from 61% to 99.65% by mass of water,
    c) - From 0.05% to 10% by mass, more particularly from 0.05% to 7.5% by mass, and even more particularly from 0.05% to 6% by mass of at least one fluorinated surfactant (ATF) chosen among nonionic surfactants and amphoteric surfactants, and
    d) - From 0.1% to 10% by mass, more particularly from 0.1% to 9% by mass, and even more particularly from 0.1% to 8% by mass of at least one gelling and / or thickening agent ( AG) chosen from xanthan gum, exudate from acacia gum, mixture of xanthan gum (G x ) and gum arabic exudate (G A ) in a mass ratio between xanthan gum (G x ) and acacia exudate gum (G A ) greater than or equal to 1/3 and less than or equal to 3/1.
    The aqueous composition (C E ) which is the subject of the present invention may optionally comprise auxiliary ingredients which are usually found in compositions intended for extinguishing fires, for example inorganic salts, salts of organic compounds, surfactants non fluorinated, urea and / or urea derivatives, solvents, antioxidants, preservatives, anticorrosion agents.
    The term “inorganic salts” denotes heteropolar compounds the crystal lattice of which comprises the participation of at least one type of cation different from the hydrogen ion and at least one type of anion different from the hydroxide ion, such as the salts constituted by a cation which is the ammonium ion or a metal cation and by an anion selected from the elements of the group consisting of halides, carbonates, bicarbonates, phosphates, nitrates, borates and sulfates, and more particularly sodium, magnesium or calcium chlorides; aluminum, barium, ammonium or hepta-hydrated zinc sulphates, mixed aluminum and potassium sulphate; manganese or zinc aluminum borates; strontium tetraborates, or hydrated potassium; sodium, aluminum, zinc, manganese or magnesium dihydrogen phosphates, monocalcic, monopotassium, zinc, manganese or aluminum phosphates, copper, iron, manganese nickel, zinc carbonates, beryllium, cerium, calcium, lithium, cobalt, chromium,
    2016P00666-FR of zirconium, strontium or potassium or sodium hexahydrate; calcium or strontium hydrogen phosphates; disodium hydrogen, di-manganese, or di-zinc; potassium, sodium, calcium or magnesium bicarbonates; iron, titanium, zinc or antimony oxides; ammonium iron sulfate; ammonium magnesium phosphate; magnesium hydrogen sulfate; barium strontium or magnesium hydrate metaborates; magnesium trisilicate, sodium, zirconium or magnesium nitrates, potassium metaphosphate, potassium potassium tripolyphosphate, sodium trimetaphosphate; ammonium molybdate, ammonium octamolybdate or ammonium heptamolybdate.
    By “salts of organic compounds, is meant a salt consisting of a cation which is the ammonium ion or a metal cation and by an organic anion which is an organic compound having at least one carboxylic acid function in carboxylate form or at least one function sulphonic acid in sulphonate form or at least one sulphate function, for example, ammonium, sodium, copper, magnesium or potassium citrates; calcium, copper, sodium, potassium, strontium or zinc acetates; sodium, ammonium, aluminum, manganese, or potassium oxalates.
    Among the non-fluorinated surfactants which are optionally present in the composition (C E ), there are anionic non-fluorinated, cationic non-fluorinated or non-fluorinated amphoteric surfactants. Examples of anionic non-fluorinated surfactants that may be mentioned include, for example, alkyl ether sulfates, alkyl sulfates, alkylamidoethersulfates, alkylarylpolyethersulfates, monoglycerides sulfates, alpha-olefinsulfonates, paraffinessulfonates, alkyl phosphates, alkyl etherphosphates, alkyl sulfonatesulfonyl sulfonates, alkylamidesulfonates sulfonates, alkylamidesulfonates, sulfonates alkylethersulfosuccinates, alkylamidesulfosuccinates, alkylsulfoacetates or acyllactylates of alkali metals, alkaline earth metals, ammonium, amines or amino alcohols.
    As examples of amphoteric non-fluorinated surfactants which are optionally present in the composition (C E ) which is the subject of the present invention, mention may, for example, be made of alkyl betaines, alkylamidobetaines, sultaines, alkylamidoalkylsulfobetaines, imidazoline derivatives, phosphobetaines, amphopolyacetates and amphopropionates.
    2016P00666-FR
    As examples of cationic non-fluorinated surfactants which are optionally present in the composition (C E ) which is the subject of the present invention, mention may, for example, be made of quaternary ammonium derivatives.
    As examples of solvents which are optionally present in the composition (C E ) which is the subject of the present invention, there may be mentioned for example polyhydric alcohols such as glycerol, diglycerol, triglycerol, glycerol oligomers, xylitol, erythritol , sorbitol, 2-methyl propanediol-1,3; alkoxylated polyhydric alcohols; glycols, such as butylene glycol, hexylene glycol, caprylylglycol or 1,2-octanediol or 1,2-pentanediol, pentylene glycol, monopropylene glycol, dipropylene glycol, isoprene glycol, butyldiglycol, trimethyl trimethylene glycol, polyethylene glycols molecular weight 200gmol · 1 and 8.000g.mol · 1 .
    According to a particular aspect, for 100% by mass of the composition (C E ), the solvents as described above can constitute a mass proportion greater than or equal to 0.5% and less than or equal to 10%, more particularly greater or equal to 0.5% and less than or equal to 5%, greater than or equal to 0.5% and less than or equal to 3%, greater than or equal to 0.8% and less than or equal to 3%.
    As examples of preserving agents which are optionally present in the composition (C E ) which is the subject of the present invention, mention may, for example, be made of benzoic acid, sodium benzoate, formaldehyde, dichloropene, ortho phenyl phenol, phenoxyethanol, methyl p-hydroxy benzoate, ethyl p-hydroxy benzoate, propyl ρ-hydroxy benzoate, isoproyple p-hydroxy benzoate, butyl p-hydroxy benzoate, benzyl alcohol, methylchloroisothiazolinone, methylisothiazolinone, and any chemical composition or any chemical compound making it possible to avoid bacterial proliferation or molds.
    According to a particular aspect, for 100% by mass of the composition (C E ), the preserving agents as described above can constitute a mass proportion, and used in a mass proportion greater than or equal to 0.01% and less than or equal at 3%, more particularly greater than or equal to 0.05% and less than or equal to 3%.
    As examples of anti-corrosion and / or antioxidant agents which are optionally present in the composition (C E ) which is the subject of the present invention, mention may, for example, be made of urea, alkanolamines, sodium and / or potassium salts and / or calcium from organic acids, such as for example sodium lactate, citrate
    2016P00666-EN sodium, sodium gluconate, sodium ascorbate, sodium succinate, and / or inorganic salts such as for example sodium nitrite, sodium molybdate, sodium phosphates and / or polyphosphates and or any other compound known to those skilled in the art.
    According to another aspect, the subject of the invention is the use of said surfactant mixture (Mi), or of said composition (C A ), or of said composition (C E ) as defined above, for preparing a fire-fighting emulsifier ;
    The subject of the invention is also a process for extinguishing a fire, characterized in that it comprises:
    - At least one step Aj ^ of preparation of a foam obtained by mixing a composition (C E ) as defined in any one of claims 13 or 14, with a gas or a mixture of gases, chosen from l 'air, nitrogen or carbon dioxide, followed,
    - At least one step A of bringing the foam prepared in step A ^ into contact with the burning surface.
    - The foam prepared in step Aj ^ of the process which is the subject of the present invention is generated by any foam generation system known to those skilled in the art and described in the state of the art, such as for example mechanical agitation of the aqueous composition (C E ), the bubbling of one or more gases in the aqueous composition (C E ), the use of a static ball mixer or any other device ensuring mixing between the gas or the mixture of gas and the aqueous composition (C E ), or else a device using a spray or spray nozzle.
    - The foam prepared in step Ai of the process which is the subject of the present invention can be produced by various devices known to those skilled in the art, such as, for example, injectors, lances, generators, weirs.
    According to a particular aspect, the subject of the invention is the process as defined above, characterized in that step Aj ^ consists of a step A / of diluting said composition (C E ) with water, in a volume ratio (C E ) / water of between 10/90 and 1/99, followed by a step Ai ”of mixing the diluted composition obtained at the end of step A / with a gas or a mixture of gas, chosen from air, nitrogen or carbon dioxide.
    Step A / diluting the aqueous composition (C E ) with water can be carried out by any means known to those skilled in the art, such as for example in tanks of suitable dimensions and with stirring at a speed adapted. More
    2016P00666-EN in particular, the dilution water and the aqueous composition (C E ) can be transported separately, then sent to a generator which creates the foam by mixing the dilution water and the composition (C E ) with l air, then projects it, at variable and adjustable rates, to the fire surface to be treated. In such a case, the mixture of dilution water and the aqueous composition (C E ) with the air is produced by suction of air during the expansion of the diluted foaming solution.
    In the process which is the subject of the invention, step A 2 of bringing the foam created in step Ai) or of step A / 'into contact with each other, is carried out by spraying onto the fire surface to be treated by means known to a person skilled in the art, such as a lance, a generator, a fire cannon,
    The following examples illustrate the invention without, however, limiting it.
    1) Preparation of foaming compositions
    1.1) Preparation of a solution of disodium N-cocoylglutamate [composition (Ci)].
    375 kilograms of water, 250 kilograms of monosodium sodium glutamate monohydrate are introduced into a reactor, with stirring and at a temperature of 20 ° C., then 184 kilograms of an aqueous sodium hydroxide solution at 30% by mass so as to reach a pH of 12. Then 245 kilograms of cocoyl chloride are added gradually with stirring, which is a mixture of acid chlorides comprising for 100% by mass 8% by mass of octanoyl chloride, 8% by mass of decanoyl chloride, 50 % by mass of lauroyl chloride, 17% by mass of myristoyl chloride, 8% by mass of palmitoyl chloride, 3% by mass of stearoyl chloride, 4% by mass of oleoyl chloride and 2% by mass of linoleoyl chloride, then 140 additional kilograms of the 30% sodium hydroxide solution to maintain the pH between 11 and 12. The temperature is maintained between 20 ° C and 50 ° C for two hours.
    The mixture obtained is acidified by adding 54 kilograms of an aqueous solution of sulfuric acid at 70% by mass, then diluted with 193 kilograms of water to obtain an aqueous solution of disodium N-cocoylglutamate [composition (Ci)].
    1.2) Preparation of an aqueous solution of disodium N-cocoylglutamate [composition (Ci)].
    The operating mode of the process described in example 1.1 is implemented by replacing the 54 kilograms of sulfuric acid at 70% by mass with 69 kilograms
    2016P00666-FR of citric acid at 80% by mass, to obtain an aqueous solution of disodium N-cocoylglutamate [composition (C /)].
    1.3) Analytical characteristics of the solutions previously prepared.
    The analytical characteristics of the compositions (Ci) and (C /) are recorded in Table 1 below.
    (This) (This') Appearance at 20 ° C (Visual method) Crystal clear Crystal clear Water mass content (a) (According to standard NFT 73-201) 68.00% 66.80% Residual fatty acids (b) (Gas Chromatography (GC)) 5.8% 5.85% PH 6.3 6.3 Sodium chloride content (Potentiometry (c) 3.60% 3.00% Sodium sulphate content (d) (Calculation on charge) 5.20% 0% Citrate content (e) (Load calculation) 0% 5.55% Mass content of active ingredient (MAO (cocoyl glutamate) (MAO = 1θθ% - (θ) - (b) - (c) - (d) - (e) 17.40% 18.80%
    Table 1
    2) Preparation of surfactant compositions based on alkvlpolyglycosides
    2.1) Preparation of a composition (C 3 )
    Poured with stirring into a reactor maintained at 80 ° C., 3.7 molar equivalents of a mixture of fatty alcohols (NO consisting for 100% of its mass of 68% by mass of dodecanol-1, of 25% by mass of tetradecanol -1 and 7% by mass of hexadecanol-1, then 1 molar equivalent of anhydrous glucose, followed by 0.15% by mass of 98% sulfuric acid per 100% by mass of the mixture.
    The reaction medium is placed under partial vacuum of approximately 0.18 × 10 5 Pa (180 mbar) and maintained at 100 ° C-105 ° C for four hours with distillation of the water formed.
    After cooling to 85 ° C-90 ° C and neutralization by adding 40% sodium hydroxide, the reaction medium thus obtained is drained at 70 ° C and filtered to remove the grains of unreacted glucose.
    The filtrate is then poured into another reactor and the excess of the fatty alcohol mixture (NO removed by distillation using a thin film film evaporator, then the residue diluted in water. After stirring for thirty minutes at 50 ° C, we get the
    2016P00666-EN composition (C 3 ), which comprises 49% by mass of water and 51% by mass of a mixture of alkyl polyglucosides (MAapgi), for which the proportions of alkyl polyglucosides and the average degree of polymerization of their polyglucoside residue are determined by gas chromatography (GC); it thus comprises for 100% by mass 69% by mass of n-dodecyl polyglucosides, 25% by mass of n-tetradecyl polyglucosides and 6% by mass of n-hexacyl polyglucosides with a degree of polymerization equal to 1.25.
    2.2) Preparation of a composition (C 4 ) comprising n-heptyl polyglucoside
    2.7 molar equivalents of heptanol-1 are added with stirring to a reactor maintained at 40 ° C., then 1 molar equivalent of anhydrous glucose, followed by 0.15% by mass of 98% sulfuric acid per 100% by mass of the mixture.
    The reaction medium is placed under partial vacuum of approximately 0.18 × 10 5 Pa (180 mbar) and maintained at 100 ° C-105 ° C for four hours with distillation of the water formed.
    After cooling to 85 ° C-90 ° C and neutralization by adding 40% sodium hydroxide, the reaction medium thus obtained is drained at 70 ° C and filtered to remove the grains of unreacted glucose.
    The filtrate is then poured into another reactor and the excess of heptanol distilled under partial vacuum, then the residue diluted in water.
    After stirring for 30 minutes at 50 ° C., the composition (C 4 ) is obtained comprising 40% by mass of water and 60% by mass of n-heptyl polyglucosides (MA A pg2), with a degree of polymerization, determined by GPC, equal to 1.25.
    2.3) Preparation of a comparative composition (C 5 ) comprising n-octyl-polyglucoside and n-decyl polyglucoside.
    2.7 molar equivalents of a mixture of fatty alcohols (N 3 ) consisting, for 100% of its mass of 50% by weight of octanol-1 and 50% by mass, are poured with stirring into a reactor maintained at 80 ° C. of decanol-1, then 1 molar equivalent of anhydrous glucose, followed by 0.15% by mass of 98% sulfuric acid per 100% by mass of the mixture.
    The reaction medium is placed under partial vacuum of approximately 0.18 × 10 5 Pa (180 mbar) and maintained at 100 ° C-105 ° C for four hours with distillation of the water formed.
    After cooling to 85 ° C-90 ° C and neutralization by adding 40% sodium hydroxide, the reaction medium thus obtained is drained at 70 ° C and filtered to remove the grains of unreacted glucose.
    2016P00666-FR
    The filtrate is then poured into another reactor, the excess of the mixture of fatty alcohols (N 3 ) removed by distillation using a thin film film evaporator, then the residue diluted in water.
    After stirring for thirty minutes at 50 ° C., the composition (C 5 ) is obtained, which comprises 40% by mass of water and 60% by mass of a mixture of alkyl polyglucosides (MA A pg3) for which the proportions in alkyl polyglucosides and the average degree of polymerization of their polyglucoside residue are determined by CPG; it thus comprises for 100% by mass 52% by mass of n-octyl polyglucoside and 48% by mass of n-decyl polyglucoside, with an average degree of polymerization equal to 1.30.
    3) Preparation of compositions according to the invention and of comparative compositions
    Six compositions (Ti) i nv ., (T 4 ) inv. and (T 5 ) inv. according to the invention, (T 2 ) comp., (T 3 ) com P. and (T 6 ) comp. comparison by pouring, with stirring, into a reactor maintained at 40 ° C., one of the compositions (C ^ or (Cf) and at least one of the compositions (C 3 ), (C 4 ) or 15 (C 5 ). The mixture is stirred for thirty minutes to obtain one of the compositions (Ti) inv A (T 6 ) comp .. es the quantities used are listed in Table 2 below:
    2016P00666-FR
    Amounts used (This) (VS/) (C 3 ) (C 4 ) (C 6 ) (Ti) înv. 0.0g 90.8g 9.2g 0.0g 0.0g (T2) comp. 0.0g 95.4g 0.0g 4.6g 0.0g (Tsjcomp. 0.0g 92.1g 0.0g 0.0g 7.9g (T 4 ) jnv. 0.0g 92.0g 7.3g 0.7g 0.0g (Tsjinv. 93.0g 0.0g 7g 0.0g 0.0g (Teicomp. 93.1g 0.0g 0.0g 6.9g 0.0g
    Table 2
    The analytical characteristics of the compositions (ΤΟ ™., (Τ 4 ) ί ην ., (T 5 ) in v., (T 2 ) com P. , (T 3 ) C omp. And (T 6 ) com P. Are listed in Table 3 below.
    AG (1) T < 2 >H 2 O (%) Aspect (Ti) înv. 5.3% 78% 22% 73.5% Homogeneous (T2) com p. 5.6% 84% 16% 73.6% Homogeneous (Tsjcom p. 5.4% 78% 22% 73.1% Homogeneous (T 4) inv. 5.4% 80% 20% 73.7% Homogeneous (T s) inv. 5.4% 78% 22% 78.7% Homogeneous (Teicom p. 5.4% 81% 29% 77.1% Homogeneous Your bleau 3
    (1): Residual fatty acids (Mass percentage) (2): T = (MAÔ / [(MAfi + (MA APG i) + (MA APG2 ) + (MA APG3 )] (3): T '= [(MA APG i) + (MA APG2 ) + (MA APG 3)] / [(MAi) + (MA APG i) + (MA APG2 ) + (MA APG 3)]
    4) Evaluation of foaming properties
    4.1) Principle of the evaluation method
    The evaluation of the foaming properties of the compositions tested is carried out by formation of a foam, from an OMS hard water solution comprising a predetermined mass content of the compositions tested, by mechanical stirring at a temperature of 20 ° C.
    4.2) Experimental protocol
    2016P00666-FR
    250 cm 3 aqueous solutions are prepared so as to obtain solutions at 0.5% by mass of surfactant active material in WHO hard water, from the compositions (Ti) j n v, (T2) comp., (Tsjcomp ., (T 4 ) inv., (Ts) inv., (Ts) comp., (Ci), (CQ, (C3) and (C4).
    An aqueous solution of 250 cm 3 at 0.39% of surfactant active material is also prepared in WHO hard water, from the compositions (Ci), (Ci '), as well as an aqueous solution of 250 cm 3 to 0.11% of active surface-active material in WHO hard water, from composition (Ci).
    WHO hard water contains, for one liter of deionized water, 0.403 grams of anhydrous calcium chloride and 0.139 grams of magnesium chloride hexahydrate; which gives it a hardness title equal to 34 ° Th.
    These solutions are poured into a 500 cm 3 beaker and then they are stirred using a Rayneri ™ laboratory motor (model 33/300) equipped with a butterfly blade with three hollow branches at a constant speed of 3,000 revolutions. per minute for two minutes.
    4.3- Expression of results
    For each test, the following parameters are measured:
    - The expansion time (Τ ωδ ): this is the duration of agitation at the end of which the suppression of the vortex in the beaker is observed. Beyond this time, the foam completely surrounds the stem of the pale and its level is horizontal;
    - The half-life time (T 1/2 ): this is the time at the end of which the foam obtained from a certain volume of foaming solution has spun an amount of solution corresponding to the half of the initial volume. For this test, the half-life time is reached when the upper level of the spin water reaches the 125 cm 3 mark on the beaker;
    - The height of foam generated by agitation (H t0 ): this is the height of foam generated at the end of the two minutes of agitation;
    - The height of residual foam after thirty minutes (H t30 ): this is the height of foam observed after thirty minutes following the end of the two-minute agitation.
    - The difference Δ Η = (H t0 - H t30 ) makes it possible to compare the quality of the foams generated by the various surfactants.
    - The consistency of the foam (μ): this is the viscosity value measured on the foam generated at a determined time, using a Rheovisco ™ RV8 viscometer equipped with the rotating disc module No. 3.
    2016P00666-FR
    - The expansion rate (T F ): this is the value of the ratio between the volume of foam (V m ) produced by a foaming composition over the volume (V s ) of the foaming solution used (water and foam concentrate) .
    4.4- Results obtained
    The results obtained for the aqueous solutions of active material in hard water WHO for the compositions (Ti) ™., (T 2 ) com P. , (T 3 ) com P. , (T 4 ) in v., ( T 5 ) inv., (T 6 ) com P. , (Ci), (Ci), (C 3 ) and (C 4 ), are indicated in Table 4 below.
    (Once) (T1 / 2) (H to ) (Htso) (ΔΗ) (Tf) μ to t = 0 (in mPas) μ at t = 30 min (in mPas) 0.50% (Ti) înv. 14s 37mn 150cm 130cm 20cm 6.6 6.370 6.080 CGJcomp. 36s 52mn 135cm 130cm 5cm 6.7 6.550 5.040 (T 3 ) comp. 19s 17mn 145cm 115cm 30cm 6.5 6.820 2.110 (T 4 ) jnv. 11s 42mn 150cm 130cm 20cm 6.6 6.880 5,970 (Ts) inv. 9s 39mn 155cm 135cm 20cm 6.8 8.100 5,950 (Teicomp. 44s 30mn 125cm 115cm 10cm 6.8 5.060 4.350 (This) 27s 37mn 145cm 120cm 25cm 6.4 7.140 5.530 (This') 37s 58min 140cm 120cm 20cm 5.3 6,230 4.290 (C 3 ) > 2mn n.m. n.m. n.m. n.d. n.m. n.m. n.m. (C 4 ) > 2mn n.m. n.m. n.m. n.d. n.m. n.m. n.m. 0.39% (This) 50s 43mn 140cm 120cm 20cm 6.1 6.640 4,870 (This') > 2mn n.m. n.m. n.m. n.d. n.d. n.m. n.m. 0.11% (C 3 ) > 2mn n.m. n.m. n.m. n.d. n.d. n.m. n.m.
    Table 4
    n.m. : Unmeasurable; n.d .: not determined
    4.5 - Analysis of the results
    These results show that the compositions according to the invention make it possible to prepare foams having all the qualities required to be used to fight fires, unlike the comparative ones.
    2016P00666-FR
    5) Examples of formulation
    The proportions in constituents are expressed in percentage by mass.
    5.1 - ARAFFF type fire-fighting foam concentrate
    Formula
    Monopropylene Glycol: 10% Rhodopol ™ 23 (1) Sipol ™ C 12 -C 14 (2) Composition (T 5 ) in v. Forafac ™ 1157 (3) Forafac ™ 1157 N <4) 1%1%10%2%2% Urea 10% Sea water QSP100%
    (1) Rhodopol ™ 23 Xanthan gum sold by the company Rhodia, (2) Sipol ™ C 12 -C 14 , mixture of fatty alcohols comprising, by weight, 85% of alcohol in C 12 and 15% of alcohol in C 14 , marketed by the company BASF, (3) and (4): amphoteric fluorinated surfactants, manufactured by the company Arkema with the general formula: C n F2n + i-CH 2 -CH2-SO 2 -NH-CH 2 -CH 2 -CH 2 -N + (CH3) 2-CH 2 -COO ·
    5.2 - ARAFFF type fire-fighting foam concentrate
    Formula
    Monopropylene Glycol: 10% SOLAGUM ™ AX <5) Sipol ™ C 12 -C 14 (2) Composition (T 5 ) in v. Forafac ™ 1157 <3) Forafac ™ 1157 N (4) 1.2%1%10%2%2% Urea 10% Sea water QSP100%
    (5): Solagum ™ AX (INCI name: Acacia Senegal gum & xanthan gum) is an emulsifying agent sold by the company SEPPIC.
    2016P00666-FR
    权利要求:
    Claims (17)
    [1" id="c-fr-0001]
    1 - Surfactant mixture (Mi), characterized in that it comprises for 100% of its mass:
    (i) - From 50% to 99% by mass, of a composition (Ci) comprising for 100% of its mass:
    (a) - From 65% to 90% by mass of at least one compound of formula (I): R 1 -C (= O) -NH-CH (COOH) - (CH 2 ) 2 -COOH (I) under acid form, partially or totally salified in which the group R 1 -C (= O) -represents a linear or branched acyl radical, saturated or unsaturated, comprising from eight to eighteen carbon atoms, and (β) - From 10 % to 35% by mass, of at least one compound of formula (II): R r C (= O) -OH (II) in acid form, partially or totally salified, in which the group Ri is as defined for formula (I), (ii) - From 1% to 50% by mass of a composition (C 2 ) comprising for 100% of its mass:
    (γ) - From 37.5% to 100% by mass of a composition (C 3 ) or of a mixture of compositions (C 3 ), said composition (C 3 ) being represented by formula (III):
    R 3 -O- (G 3 ) p -H (III) in which R 3 represents a linear or branched, saturated or unsaturated aliphatic radical containing from 12 to 16 carbon atoms, G 3 represents the remainder of a reducing sugar and p represents a decimal number greater than or equal to 1.05 and less than or equal to 5, said composition (C 3 ) consisting of a mixture of compounds represented by the formulas (llh), (lll 2 ), (lll 3 ), (lll 4 ) and (lll 5 ):
    R 3 -O- (G 3 ) iH (llh), R 3 -O- (G 3 ) 2 -H (llh), R 3 -O- (G 3 ) 3 -H (iih), R 3 -O- (G 3 ) 4 -H (llh), R 3 -O- (G 3 ) 5 -H (He h),
    in the respective molar proportions ai, a 2 , a 3 , a 4 and a 5 , such that:
    the sum: ai + a 2 + a 3 + a 4 + a 5 is equal to 1, and the sum ai + 2a 2 + 3a 3 + 4a 4 + 5a 5 is equal to p;
    (δ) - From 0% to 37.5% by mass of at least one alcohol of formula (IV):
    2016P00666-FR
    R 3 -OH (IV) in which R 3 is as defined for the preceding formula (III), (ε) - From 0% to 12.5% of a composition (C 4 ) or of a mixture of compositions (C 4 ), said composition (C 4 ) being represented by formula (V):
    R 4 -O- (G 4 ) q -H (V) in which R 4 represents a linear aliphatic radical, chosen from butyl, pentyl, hexyl, heptyl and (2-ethyl hexyl) radicals, G 4 represents the residue d a reducing sugar and q represents a decimal number greater than or equal to 1.05 and less than or equal to 5, said composition (C 4 ) consisting of a mixture of compounds represented by the formulas (V,), (V 2 ), (V 3 ), (V 4 ) and (V 5 ):
    R 4 -O- (G 4 ) iH (Vi), R 4 -O- (G 4 ) 2 -H (V 2 ), R 4 -O- (G 4 ) 3 -H (V 3 ), R 4 -O- (G 4 ) 4 -H (V 4 ), R 4 -O- (G 4 ) 5 -H (V 5 ),
    in the respective molar proportions aj, a ' 2 , a' 3 , a ' 4 and a' 5 , such that:
    the sum: aj + a ' 2 + a' 3 + a ' 4 + a' 5 is equal to 1, and the sum aj + 2a ' 2 + 3a' 3 + 4a ' 4 + 5a' 5 is equal to q; and (η) - From 0% to 12.5% by mass of at least one alcohol of formula (VI):
    R 4 -OH (VI) in which R 4 is as defined for the preceding formula (V).
    [2" id="c-fr-0002]
    2 - Mi surfactant mixture as defined in claim 1, characterized in that in the formulas (I) and (II) the group Ri-C (= O) - represents an acyl radical chosen from octanoyl, decanoyl and dodecanoyl radicals , tetradecanoyl, hexadecanoyl, octadecanoyl, 9-octadecenoyl, 9,12-octadecadienoyl and 9,12,15-octadecatrienoyl.
    [3" id="c-fr-0003]
    3 - Surfactant mixture (Mi) as defined in any one of claims 1 or 2, characterized in that said composition (C 2 ) comprises for 100% of its mass:
    (y) - A mass proportion in said composition (C 3 ) greater than or equal to 70% and less than 100%, and (δ) - A mass proportion in said alcohol of formula (IV) greater than or equal to 0% and less or equal to 7.5%,
    2016P00666-FR (ε) - A mass proportion in said composition (C 4 ) greater than or equal to 0% and less than or equal to 20%, and (η) - A mass proportion in said alcohol of formula (VI) greater than or equal at 0% and less than or equal to 2.5%.
    [4" id="c-fr-0004]
    4 - Surfactant mixture (M ^ as defined in any one of Claims 1 to 3, characterized in that in formula (III), G 3 represents the remainder of a reducing sugar chosen from the remains of glucose, xylose and arabinose.
    [5" id="c-fr-0005]
    5 - Surfactant mixture (Mi) as defined in any one of claims 1 to 4, characterized in that in formula (III), p represents a decimal number greater than or equal to 1.05 and less than or equal to 2.5.
    [6" id="c-fr-0006]
    6 - Surfactant mixture (M ^ as defined in any one of Claims 1 to 5, characterized in that in the formulas (III) and (IV), R 3 represents a linear alkyl radical chosen from the dodecyl radicals, tetradecyl and hexadecyl.
    [7" id="c-fr-0007]
    7 - Surfactant mixture (Mi) as defined in any one of claims 1 to 6, characterized in that in formula (V), G 4 represents the remainder of a reducing sugar chosen from the remains of glucose, xylose and arabinose.
    [8" id="c-fr-0008]
    8 - Surfactant mixture (M ^ as defined in any one of Claims 1 to 7, characterized in that in the formula (V), q represents a decimal number greater than or equal to 1.05 and less than or equal to 2.5.
    [9" id="c-fr-0009]
    9 - Surfactant mixture (M ^ as defined in any one of Claims 1 to 8, characterized in that in the formulas (V) and (VI), R 4 represents a linear alkyl radical chosen from the hexyl, heptyl radicals and (2-ethyl hexyl).
    [10" id="c-fr-0010]
    10 - Surfactant mixture (M ^ as defined in any one of claims 1 to 9, characterized in that said composition (C 2 ) comprises a mixture of compositions (C 3 ) and compositions (C 4 ), said mixture comprising for 100% of its mass:
    2016P00666-FR (γι) - From 30% to 90% by mass of a composition (C 3 ) represented by the formula (III) in which R 3 represents the dodecyl radical, (γ 2 ) - From 9% to 40% by mass of a composition (C 3 ) represented by the formula (III) in which R 3 represents the tetradecyl radical, and (γ 3 ) - - From 1% to 10% by mass of a composition (C 3 ) represented by the formula (III) in which R 3 represents the hexadecyl radical, (ej) - From 0% to 20% by mass of a composition (C 4 ) represented by the formula (V) in which R 4 represents the heptyl radical.
    [11" id="c-fr-0011]
    11 - Surfactant mixture (M ^ as defined in any one of claims 1 to 10, characterized in that the mass ratio:
    Δ = Mass of compound (s) of formula (I) / [Mass of the composition (C 3 ) + Mass of the composition (C 4 )], is greater than or equal to 65/35 and less than or equal to 90/10 .
    [12" id="c-fr-0012]
    12 - Composition (C A ) characterized in that it comprises for 100% by mass:
    a) - From 5% to 85% by mass of said (M ^ as defined in any one of Claims 1 to 11, and
    b) - From 15% to 95% by mass of water.
    [13" id="c-fr-0013]
    13 - Composition (C E ) characterized in that it comprises for 100% by mass:
    a) - From 0.1% to 25% by mass of said mixture (M ^ as defined in any one of claims 1 to 11,
    b) - From 55% to 99.75% water,
    c) - From 0.05% to 10% by mass of at least one fluorinated surfactant (ATF) chosen from anionic, cationic, nonionic and amphoteric fluorinated surfactants,
    d) - From 0.1% to 10% by mass of at least one gelling and / or thickening agent (AG) chosen from polysaccharides consisting of derivatives of oses, polysaccharides consisting solely of oses, cellulose and derivatives of cellulose, starches and polyelectrolytes which are linear or branched or crosslinked.
    [14" id="c-fr-0014]
    14 - Composition (C E ) as defined in claim 13 characterized in that it comprises for 100% of its mass:
    a) - From 0.1% to 25% by mass of said mixture (M ^ in which:
    2016P00666-FR
    - The compound of formula (I) is chosen from monosodium N-cocoyl glutamate, monopotassium N-cocoyl glutamate, disodium N-cocoyl glutamate, dipotassium N-cocoyl glutamate,
    - The compound of formula (II) is chosen from sodium cocoate and potassium cocoate,
    - In formula (III), R 3 represents a linear or branched, saturated or unsaturated aliphatic radical, comprising from 12 to 16 carbon atoms, G 3 represents the remainder of glucose or xylose and p represents a decimal number greater than or equal 1.05 and less than or equal to 2.5;
    - In formula (IV), R 3 represents a linear or branched, saturated or unsaturated aliphatic radical, comprising from 12 to 16 carbon atoms,
    - In formula (V), R 4 represents an aliphatic radical, chosen from the n-heptyl and 2-ethyl hexyl radicals, G 4 represents the remainder of glucose or xylose and q represents a decimal number greater than or equal to 1, 05 and less than or equal to 2,
    - In formula (VI), R 4 represents an aliphatic radical, chosen from the n-heptyl and 2-ethyl hexyl radicals.
    b) - From 55% to 99.75% water,
    c) - From 0.05% to 10% by mass of at least one fluorinated surfactant (ATF) chosen from nonionic and amphoteric fluorinated surfactants,
    d) - From 0.1% to 10% by mass of at least one gelling and / or thickening agent (AG) chosen from xanthan gum, the exudate of acacia gum, the mixture of xanthan gum ( G x ) and gum arabic exudate (G A ) in a mass ratio between xanthan gum (G x ) and acacia exudate gum (G A ) greater than or equal to 1/3 and less or equal to 3/1.
    [15" id="c-fr-0015]
    15 - Use of the surfactant mixture (Mi) as defined in any one of claims 1 to 11 of the composition (C A ) as defined in claim 12 or of the composition (C E ) as defined in any of claims 13 or 14 as a component of a fire fighting foam concentrate.
    [16" id="c-fr-0016]
    16 - Method for extinguishing a fire, characterized in that it comprises:
    2016P00666-FR
    - At least one step Aj ^ of preparation of a foam obtained by mixing a composition (C E ) as defined in any one of claims 13 or 14, with a gas or a mixture of gases, chosen from l 'air, nitrogen or carbon dioxide, followed,
    - At least one step A for bringing the foam prepared in step A ^ 5 into contact with the burning surface.
    [17" id="c-fr-0017]
    17 - Process as defined in claim 16, characterized in that step Α 4 consists of a step A / of diluting said composition (C E ) with water, in a volume ratio (C E ) / water between 10/90 and 1/99, followed by a step A / 'of mixing 10 of the diluted composition obtained at the end of step Af with a gas or a mixture of gases, chosen from air , nitrogen or carbon dioxide.
    类似技术:
    公开号 | 公开日 | 专利标题
    FR3061025A1|2018-06-29|NOVEL SURFACE MIXTURE, NOVEL COMPOSITION COMPRISING THE SAME AND USE THEREOF IN EMULSIONS FOR COMBATTING FIRES
    EP0660999B1|1999-05-12|Guar gum as drift control agent
    CA2562996C|2013-11-26|Novel high molecular weight associative amphoteric polymers and uses thereof
    EP0001192B1|1981-12-23|Gel forming compositions based on galactomannans and de-acetylated xanthanand process for obtaining them.
    JP6824166B2|2021-02-03|Water-enhanced fire-suppressing hydrogel
    EP2923739A1|2015-09-30|Aqueous compositions for extinguishing fire
    AU2017302283B2|2021-06-10|Firefighting foam compositions containing deep eutectic solvents
    US10293279B2|2019-05-21|Foam control formulations
    FR2734737A1|1996-12-06|FOAMING COMPOSITION AND ITS USE AS A FIRE-FIGHTING EMULSE
    KR101723833B1|2017-04-06|Foam extinguishing composition of multipurpose and environment-friendly
    WO2018234647A1|2018-12-27|New surfactant mixture, new composition comprising same, and use thereof in foam liquids for fighting fires
    US20210187337A1|2021-06-24|Systems and compositions for suppressing and extinguishing fires
    WO2013030499A2|2013-03-07|Novel method for improving the foaming properties of cleaning compositions for topical use
    EP2198932A2|2010-06-23|Use of amphoteric tensides for creating foam
    EP3863404A1|2021-08-18|Composition for decontaminating solid surfaces
    FR2637506A1|1990-04-13|New emulsifying liquids for the production of extinguishing foam; their production and their use
    FR3070043B1|2019-08-16|FORMULATION CONTAINING AN ASSOCIATIVE POLYMER
    FR3087089A1|2020-04-17|DISINFECTANT COMPOSITION FOR TOPICAL USE
    JP2019058279A|2019-04-18|Water addition type fire extinguisher, and fire extinguishing method of peat fire
    CA3080853A1|2020-11-21|Suppression of fire
    同族专利:
    公开号 | 公开日
    CN110249038A|2019-09-17|
    US20190314660A1|2019-10-17|
    JP2020513890A|2020-05-21|
    CN110249038B|2021-11-26|
    FR3061025B1|2019-01-25|
    CA3047853A1|2018-06-28|
    AU2017383280A1|2019-07-18|
    WO2018115635A1|2018-06-28|
    EP3559181A1|2019-10-30|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO1992015371A1|1991-03-11|1992-09-17|Chubb National Foam, Inc.|Alcohol resistant aqueous film forming firefighting foam|
    EP2468842A1|2010-12-21|2012-06-27|Johnson & Johnson Consumer Companies Inc.|Compositions comprising polyglyceryl nonionic surfactants|
    FR2969639A1|2010-12-23|2012-06-29|Seppic Sa|NEW PROCESS FOR DRILLING UNDERGROUND CAVITIES|
    FR3016883A1|2014-01-24|2015-07-31|Seppic Sa|METHOD FOR IMPROVING THE FOAMING PROPERTIES OF A CLEANING FORMULATION, NEW CLEANING COMPOSITIONS AND THEIR USE FOR CLEANING THE SURFACES|CN108126293A|2017-12-06|2018-06-08|田秋珍|A kind of compound protein fire foam|US4096326A|1976-10-13|1978-06-20|Hercules Incorporated|Dihydroxypropyl cellulose|
    US4999119A|1989-07-20|1991-03-12|Chubb National Foam, Inc.|Alcohol resistant aqueous film forming firefighting foam|
    WO1992004942A1|1990-09-19|1992-04-02|Atlantic Richfield Company|High-stability foams for long-term suppression of hydrocarbon vapors|
    FR2734737B1|1995-06-01|1997-07-11|Seppic Sa|FOAMING COMPOSITION AND ITS USE AS A FIRE-FIGHTING EMULSE|
    JPH0970528A|1995-06-30|1997-03-18|Ajinomoto Co Inc|Surfactant|
    WO1998009611A1|1996-09-09|1998-03-12|Societe D'exploitation De Produits Pour Les Industries Chimiques - Seppic|Cosmetic use of compounds with lipoaminoacid structure and cosmetic compositions with soothing activity incorporating some of these compounds|
    US6433061B1|2000-10-24|2002-08-13|Noveon Ip Holdings Corp.|Rheology modifying copolymer composition|
    GB0125685D0|2001-10-26|2001-12-19|Inst Francais Du Petrole|Drilling wells and drilling fluids|BE1025603B1|2018-02-06|2019-04-25|Uniteq S.A.|EXTINGUISHING FOAM COMPOSITION|
    FR3087090A1|2018-10-12|2020-04-17|Societe D'exploitation De Produits Pour Les Industries Chimiques Seppic|COMPOSITION FOR DECONTAMINATION OF SOLID SURFACES|
    FR3087089B1|2018-10-12|2021-01-15|Soc Dexploitation De Produits Pour Les Industries Chimiques Seppic|DISINFECTING COMPOSITION FOR TOPICAL USE|
    CN111388933B|2020-03-25|2021-08-31|国网湖南省电力有限公司|Fire extinguishing agent for cable tunnel fire, fire extinguishing system and fire extinguishing method|
    法律状态:
    2017-12-21| PLFP| Fee payment|Year of fee payment: 2 |
    2018-06-29| PLSC| Publication of the preliminary search report|Effective date: 20180629 |
    2019-12-19| PLFP| Fee payment|Year of fee payment: 4 |
    2020-12-23| PLFP| Fee payment|Year of fee payment: 5 |
    2021-12-24| PLFP| Fee payment|Year of fee payment: 6 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1663286A|FR3061025B1|2016-12-23|2016-12-23|NOVEL SURFACE MIXTURE, NOVEL COMPOSITION COMPRISING THE SAME AND USE THEREOF IN EMULSIONS FOR COMBATTING FIRES|
    FR1663286|2016-12-23|FR1663286A| FR3061025B1|2016-12-23|2016-12-23|NOVEL SURFACE MIXTURE, NOVEL COMPOSITION COMPRISING THE SAME AND USE THEREOF IN EMULSIONS FOR COMBATTING FIRES|
    PCT/FR2017/053509| WO2018115635A1|2016-12-23|2017-12-12|Novel surfactant mixture, novel composition comprising same and use thereof in foam liquids for fighting fires|
    CA3047853A| CA3047853A1|2016-12-23|2017-12-12|Novel surfactant mixture, novel composition comprising same and use thereof in foam liquids for fighting fires|
    JP2019533375A| JP2020513890A|2016-12-23|2017-12-12|Novel surfactant mixtures, novel compositions containing them and their use in fire fighting foam concentrates|
    US16/473,135| US20190314660A1|2016-12-23|2017-12-12|Novel surfactant mixture, novel composition comprising same and use thereof in foam liquids for fighting fires|
    EP17822401.0A| EP3559181A1|2016-12-23|2017-12-12|Novel surfactant mixture, novel composition comprising same and use thereof in foam liquids for fighting fires|
    CN201780085602.3A| CN110249038B|2016-12-23|2017-12-12|Novel surfactant mixtures, novel compositions comprising the same and their use in foam concentrates for extinguishing fires|
    AU2017383280A| AU2017383280A1|2016-12-23|2017-12-12|Novel surfactant mixture, novel composition comprising same and use thereof in foam liquids for fighting fires|
    [返回顶部]