EP2198932A2 - Utilisation de tensioactifs amphotères pour la production de mousse - Google Patents

Utilisation de tensioactifs amphotères pour la production de mousse Download PDF

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Publication number
EP2198932A2
EP2198932A2 EP09176044A EP09176044A EP2198932A2 EP 2198932 A2 EP2198932 A2 EP 2198932A2 EP 09176044 A EP09176044 A EP 09176044A EP 09176044 A EP09176044 A EP 09176044A EP 2198932 A2 EP2198932 A2 EP 2198932A2
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EP
European Patent Office
Prior art keywords
glycol
composition according
ether
foam
component
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP09176044A
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German (de)
English (en)
Inventor
Berend-Jan De Gans
Annika Trosin
Dirk Kuppert
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Evonik Goldschmidt GmbH
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Evonik Goldschmidt GmbH
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Publication of EP2198932A2 publication Critical patent/EP2198932A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
    • A62D1/0028—Liquid extinguishing substances
    • A62D1/0035—Aqueous solutions
    • A62D1/0042—"Wet" water, i.e. containing surfactant
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
    • A62D1/0071—Foams
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
    • A62D1/0071—Foams
    • A62D1/0085—Foams containing perfluoroalkyl-terminated surfactant

Definitions

  • the invention relates to foam-forming aqueous compositions containing amphoteric surfactants and fatty acids and their use.
  • Aqueous foams are suitable for a variety of applications, for example in the field of cosmetics for the production of shaving or hair care products, domestic or industrial cleaning, suppression of dust, papermaking, dyeing, fractionation or separation of metals or their salts, for Isolation of ice surfaces, concrete or cement production, protection of surfaces, structures or vegetation against fire and / or heat, for fire fighting, including fires in mines, and for frost protection of plants.
  • applications for example in the field of cosmetics for the production of shaving or hair care products, domestic or industrial cleaning, suppression of dust, papermaking, dyeing, fractionation or separation of metals or their salts, for Isolation of ice surfaces, concrete or cement production, protection of surfaces, structures or vegetation against fire and / or heat, for fire fighting, including fires in mines, and for frost protection of plants.
  • foams for applications where the foam contacts non-aqueous liquids, such as organic solvents or petrochemical fuels, and where the foam must have sufficient stability and flowability.
  • non-aqueous liquids such as organic solvents or petrochemical fuels
  • foams must have sufficient stability and flowability.
  • These applications include the cleaning of facilities such as tank farms, pipes, pipelines or boilers, the reduction of evaporation losses of volatile hydrocarbons or other organic solvents, or the firefighting.
  • foam blankets are also suitable for preventing the occurrence of fires.
  • foaming agents are usually used, which are based on the Spit surfaces of flammable liquids spontaneously and form a thin, water-containing film between foam and flammable liquid ("Aqueous Film Forming Foam" - AFFF or A3F). This film ensures the rapid spread of the foam and a vapor-tight barrier, preventing re-ignition.
  • AFFFs contain surfactants with perfluorinated groups.
  • foaming agent compositions are for example in the publications DE-1 216 116 . EP-A-0 595 772 . US 4,420,434 . DE-2 357 281 described.
  • perfluorinated surfactants relate to the control of solid fires.
  • a surfactant is added to the extinguishing water. Examples of such surfaces are plastic, waxed paper or hard coal.
  • the addition of a surfactant improves the wetting effect or the penetration depth of the extinguishing water, and thus the effectiveness with the hydrophobic solids can be cooled.
  • foaming or wetting agents which are suitable for combating solvent, fuel, fuel or solid fires and which manage without or at least with a significantly reduced proportion of surfactants having perfluorinated groups.
  • Highly foaming surfactants are, for example, the so-called amphoteric surfactants, also called amphoteric surfactants or ampholytic surfactants. These are surfactants which are anionic or cationic depending on the pH. Examples of amphoteric surfactants are amphoacetates and amphodiacetates, amphopropionates and amphodipropionates, hydroxysultaines, glycinates, amine oxides, betaines and sulfobetaines. A particular class of amphoteric surfactants are the sulfobetaines and the betaines which exist in solution at neutral pHs as zwitterionic surfactants. The prior art relating to the use of organic, amphoteric surfactants for fire fighting is summarized here.
  • WO-9927373 are surfactant concentrates containing partly a surfactant from the group of Hydroxysultaine, dipropionates and propionates, diacetates and acetates, betaines, Amidopropylsultaine and hydroxy-substituted, amphoteric sulfonates, and partly a perfluorinated amine oxide.
  • the font WO-9746283 describes similar mixtures.
  • the value of the spreading coefficient S must be positive. Otherwise, the aqueous phase forms a lens on the flammable liquid.
  • S ⁇ oa - ⁇ wa - ⁇ ow
  • the surface tension of the flammable liquid provides an upper limit to the surface tension of a spreading aqueous solution.
  • the surface tension of flammable liquids is typically below 25 mN ⁇ m -1 at room temperature.
  • Cyclohexane for example, has a surface tension of 24.65 mN ⁇ m -1 at 25 ° C.
  • n-heptane has a surface tension of 19.65 mN ⁇ m -1 ( Source: CRC Handbook of Chemistry and Physics, 83rd Edition, CRC Press, Boca Raton, 2002 ).
  • the surface tension of solutions of organic surfactants above the critical micelle concentration is typically above 30 mN ⁇ m -1 . Pure conventional organic surfactants are therefore not able to take over the role of perfluorinated surfactants.
  • JP-51084197 is a mixture of 10 to 40 parts of C 12 -C 18 Alkyldimethylbetain, 5 to 30 parts of Al, Mg or Ca soap based on C 12 -C 18 fatty acids, 1 to 5 parts of C 12 -C 14 alkanol and solvent described Service.
  • C 12 -alkanol or lauryl alcohol is considered to be hazardous to the environment and very toxic to aquatic organisms.
  • Al, Mg or Ca soaps based on fatty acids are often used because of their defoaming action. Their use in fire-fighting foams can therefore only be recommended to a limited extent ( Source: Defoaming - Theory and Industrial Applications, Surfactant Science Series Volume 45, Marcel Dekker Inc., New York, 1993, p.204 ).
  • Particularly preferred are those from the aqueous Solutions containing the mixtures of organic surfactants according to the invention, foams obtained without the addition or at least with reduced addition of compounds with perfluorinated groups have a high stability to hydrophobic liquids.
  • the blends of organic surfactants according to the invention should preferably also be simple and inexpensive to produce.
  • the inventive task can be achieved by mixing amphoteric surfactants with carboxylic acids.
  • foam-forming compositions which as component a) are a betaine of the general formula (I), an amphoacetate of the general formula (II), or an amphodiacetate of the general formula (III) contained alone or in mixtures with one another.
  • M + is an alkali metal, ammonium and / or an organically substituted ammonium ion.
  • Preferred alkali metal are sodium and potassium.
  • the particularly preferred component a) according to the invention of the general formula (I), (II) or (III) has as radical R a saturated or unsaturated, linear or branched aliphatic carbon chain having 5 to 30 carbon atoms or a saturated or unsaturated, linear one or branched aliphatic carbon chain having inserted into the carbon chain heteroatoms having between 5 and 40 atoms in the carbon heteroatom chain, from.
  • Cocamidopropyl betaine, C 8 -C 10 alkylamidopropyl betaine, cocoamphoacetate, C 8 -C 10 alkyl amphoacetate, cocoamphodiacetate, C 8 -C 10 alkyl amphodiacetate or mixtures thereof are particularly preferably used as component a).
  • Heteroatoms can be an or multiple oxygen, nitrogen and / or sulfur atoms are present in the carbon chain.
  • Betaine, amphoacetates and amphodiacetates may contain a high salt load due to their production, which does not adversely affect the application; in particular, up to 10% by weight of sodium chloride may be contained.
  • the compounds of the formulas (I), (II) and (III) are typically technical products whose main constituents correspond to the formulas given (source: fats • soaps • paints 80, 448, 1978).
  • the carboxylic acids of component b) may, for. B. be selected from mono- or polybasic, saturated or unsaturated, linear or branched aliphatic carboxylic acids having 5 to 30 carbon atoms.
  • suitable carboxylic acids are the unbranched saturated carboxylic acids n-decanoic acid, n-dodecanoic acid, n-tetradecanoic acid, n-hexadecanoic acid and n-octadecanoic acid.
  • the carboxylic acids may be technical mixtures of molecules with different carbon chain lengths.
  • C 8 -C 10 fatty acid, n-decanoic acid, n-dodecanoic acid or mixtures thereof are particularly preferably used as the carboxylic acid (component b)).
  • the mass ratio of betaines as component a) to component b) in the concentrate in the composition according to the invention is preferably from 99% by weight to 1% by weight to 80% by weight to 20% by weight, and particularly preferred from 95 wt% to 5 wt% to 85 wt% to 15 wt%.
  • the ratio to component b) in the composition according to the invention is 80% by weight to 20% by weight to 20% by weight to 80% by weight and particularly preferably 70% by weight. from 30% to 30% by weight to 70% by weight.
  • the ratio is to component b) in the composition according to the invention 99% by weight to 1% by weight to 20% by weight to 80% by weight and particularly preferably 95% by weight to 5% by weight to 30% by weight % to 70% by weight.
  • component (c) one or more substances can be selected from the group comprising ethanol, n-propanol, isopropanol, 1,3-propanediol, 1,3-butanediol, 2,3-butanediol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, Dipropylene glycol, tripropylene glycol, propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol ethyl ether, dipropylene glycol ethyl ether, tripropylene glycol ethyl ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, tripropylene glycol ethyl ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, tripropylene glycol
  • the inventive compositions can be marketed as a solid mixture or highly concentrated aqueous solutions and then, if necessary, brought to an application concentration with (further) water having a surface tension of less than 25 mN / m.sup.- 1 at 25.degree.
  • the highly concentrated solution of the components may contain up to 75% by weight of the mixture of components a) and b) preferably, the concentration is between 20 and 65 wt .-%.
  • the solvent used is preferably water (component d)).
  • the concentrations of a) and b) and their ratio to c) and d) depend mainly on the production conditions of the amphoteric surfactant and the desired use concentrations and viscosities. The required concentrations are familiar to the person skilled in the art or easily determinable according to the intended use.
  • the typical auxiliaries and additives may be anionic, nonionic or cationic hydrocarbon surfactants, perfluorosurfactants, polymeric foam stabilizers and / or thickeners, high molecular weight acidic polymers and / or coordinating salts, antifreeze agents, sequestering agents, corrosion inhibitors, film-forming additives, preservatives, water and additives which are obvious to the person skilled in the art.
  • perfluorosurfactants can result in an extinguishing foam which, in use, has a further improved extinguishing rate and a reduced risk of re-ignition.
  • compositions of the invention preferably have less than 1.0% by weight of perfluorosurfactant, based on the weight of the composition of the invention, or less than 0.1% by weight of perfluorosurfactant in the foam, resulting from the dilution of the composition to the application concentration.
  • the teaching according to the prior art as z. As the above-mentioned writings US 3,849,315 . US 4,038,195 . US 3,957,657 and US 3,957,658 as well as the writings of the font family DE-A-28 26 224 . WO-A-80/01883 . US 4,464,267 . US 4,387,032 . US 4,060,489 . US 4,149,599 and US 4,060,132 can be removed, requires a five to tenfold concentration of surfactants with perfluorinated groups.
  • the desired surface tension at room temperature of an aqueous solution of the composition according to the invention consisting of the components a), b) and c) is below 25 mN ⁇ m -1 , disregarding the customary auxiliaries and additives (which can further lower the surface tension).
  • the foams prepared from the dilute solutions of the compositions of the invention fires can be avoided by covering the possible combustible with a foam carpet. Furthermore, even existing fires can be deleted. Particularly suitable is the foam prepared with the use of the composition according to the invention for controlling fires of hydrophobic materials, in particular liquids. In particular, fires different solvents, fuels and / or fuels or mixtures thereof with the foam, prepared with the concomitant use of the dilute aqueous solutions of the composition according to the invention, be deleted. Another application of the composition according to the invention relates to the control of solid fires. To improve the wetting effect or the penetration depth of the extinguishing water on / in hydrophobic, solid surfaces, the composition of the invention is added to the extinguishing water. Thus, the effectiveness with the hydrophobic solid can be cooled, increased.
  • the amount of active substance that is the composition of amphoteric surfactant and carboxylic acid according to the invention - that is without further customary additives and auxiliaries - in an aqueous solution to produce a surface tension of less than 25 mN / m -1 , less than 5 wt .-%, preferably less than 3.0 wt .-% and in particular less than 0.6 wt .-%.
  • Suitable extinguishing foams can then be used by methods familiar to the person skilled in the art generate, as z. In " Holger de Vries, Fire fighting with water and foam - technology and tactics, ecomed Verlagsgesellschaft AG & Co.
  • the ratio of the inventive concentrate to water is from 1% to 6% by weight.
  • the ratio of water plus surfactant concentrate to air it can be used to produce a heavy foam, a medium foam or a light foam.
  • For use as a wetting agent typically results in a ratio of the inventive concentrate to water of 0.5 wt .-% to 2 wt .-%.
  • the amount of amphoteric surfactant mixture and carboxylic acid compared to foam systems according to the prior art is significantly reduced in order to achieve at least comparable foam effect, which allows significant financial savings and a discharge of the environment.
  • compositions according to the invention have the advantage that the foam obtained therefrom is also sufficiently stable on hydrophobic and optionally combustible materials, in particular liquids, and can thus be applied to such materials.
  • the aqueous foams obtained from the compositions according to the invention are outstandingly suitable as fire-extinguishing foams or covering foams, in particular for use in the presence of hydrophobic materials, in particular hydrophobic liquids.
  • the stability of the foam prepared from the compositions according to the invention without the addition of surfactants having perfluorinated groups has the advantage that no fluoro-organic or other environmentally harmful compounds in the environment when using the composition according to the invention for the production of foam.
  • compositions according to the invention and a process for their preparation and their use are described below by way of example, without the invention being restricted to these exemplary embodiments.
  • ranges, general formulas, or classes of compounds are intended to encompass not only the corresponding regions or groups of compounds explicitly mentioned, but also all sub-regions and sub-groups of compounds obtained by removing individual values (ranges) or compounds can be. If documents are cited in the context of the present description, their contents are intended to form part of the disclosure content of the present invention.
  • compositions of the invention may be used to prepare a foam, preferably an aqueous foam.
  • the compositions according to the invention can be used in particular for the production of fire-extinguishing foams or foams for reducing evaporation losses of volatile hydrocarbons or other organic solvents and for preventing the occurrence of fires.
  • the compositions according to the invention or the mixtures of amphoteric surfactants and carboxylic acids contained in the compositions can also be used for the production of toxicologically acceptable foams for exercise purposes.
  • composition according to the invention can be used in particular for producing aqueous foam which is applied to or produced on a hydrophobic surface or a liquid, preferably on a hydrophobic liquid.
  • Another object of the invention are firefighting foams prepared using the compositions of the invention.
  • Another object of the invention are practice foams prepared using the compositions of the invention. These practice foams are free from perfluorinated surfactants, in particular for reasons of environmental protection.
  • compositions of the invention can be prepared in a variety of ways and at various concentrations. In particular, they can be prepared by mixing. Preference is given to compositions which are prepared by mixing the described amphoteric surfactants, fatty acids and solubilizers with anionic, nonionic or cationic hydrocarbon surfactants, perfluorosurfactants, polymeric foam stabilizers and / or thickeners, high molecular weight acidic polymers and / or coordinating salts, antifreezes, sequestering agents, corrosion inhibitors, film-forming agents Additives, preservatives, water and additives, which are obvious to those skilled, are used. at the concentrations taught by the references listed in this application.
  • the determination of the surface tension of the investigated foam solutions was carried out with the aid of a device of the type OCA 35 from Dataphysics Instruments GmbH, Filderstadt, and associated evaluation software.
  • This device works computer-controlled according to the principle of the pendant-drop method. This is a method for determining the surface tension of liquids against a gas phase by means of a drop hanging on a capillary. Based on the drop shape, which is dependent on the balance of forces between gravity and surface tension, and can be mathematically described using the Young-Laplace equation, the surface tension of the liquid is determined.
  • the ability of organic surfactants to produce aqueous foams was tested by determining the expansion factor.
  • the foaming number (VZ) is the ratio of the volume of the finished foam to the volume of the water-foaming agent mixture. A detailed description of this parameter can be found for example in G. Rodewald, A. Rempe: "Fire Extinguishing Agents - Properties - Effect - Application”; Kohlhammer Verlag, Stuttgart, 2005 , When performing the test was a Stirring mixer from Braun (type: Power Blend MX 2050) used.
  • the kerosene stability of the foam at room temperature was measured by applying 100 mL of jet A1 kerosene produced in 100 mL of the described manner to the foam, which was in a 10.8 cm diameter metal dish. The time to rupture of the foam blanket was measured.
  • Fresh foam produced in the manner previously described was also used to extinguish kerosene fires. This was analogous to the published patent application DE-2 240 263 a metal funnel with a funnel opening of 18 mm with the opening placed over a 10.8 cm diameter metal dish containing 100 g of Jet A1 kerosene. The kerosene was lit. After prewaxing for a maximum of 15 seconds, quenching was started by applying 100 mL of the immediately generated foam to the side.
  • the foamable aqueous composition of SYNDURA ® (from Angus Fire), a commercially available, fluorine-free surfactant concentrate for the production of fire-fighting foams represents a 6 wt .-% dilution.
  • the measured surface voltage refers in SYNDURA ® on the manufacturer's recommended dilution of 6 wt .-%.
  • the surface tension of TEGO ® Betain F50 in the mixture with lauric acid strongly depends on the mixing ratio. At a mixing ratio of 90 parts TEGO ® F50 Betaine to 10 parts of lauric acid, the surface tension reaches a minimum of 23 mN ⁇ m -1. The same applies to the surface tension of the Rewoteric® AM C. The minimum of 22.9 mN ⁇ m -1 is achieved with a mixing ratio of 50 parts of Rewoteric® AM C to 50 parts of lauric acid. SYNDURA ® shows a slightly higher surface tension at the application concentration of 6% by weight.
  • Table 3 Delete time Surfactant A Surfactant B Mixing ratio (mass ratio) Extinguishing time [s] TEGO ® Betain F50 keeps burning TEGO ® Betain F50 lauric acid 90:10 10 TEGCO ® betaine 810 Dean acid 90:10 30 Rewoteric® AM C lauric acid 70:30 1 Rewoteric® AM C lauric acid 60:40 1 Rewoteric® AM C lauric acid 50:50 1 Angus Fire Syndura ® Keep burning
  • TEGO and Rewoteric are registered trademarks of Evonik Goldschmidt GmbH, Syndura is a registered trademark of Angus Fire Corp.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Business, Economics & Management (AREA)
  • Emergency Management (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Fire-Extinguishing Compositions (AREA)
EP09176044A 2008-12-16 2009-11-16 Utilisation de tensioactifs amphotères pour la production de mousse Withdrawn EP2198932A2 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE200810054712 DE102008054712A1 (de) 2008-12-16 2008-12-16 Verwendung von amphoteren Tensiden zur Erzeugung von Schaum

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Cited By (9)

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WO2016127193A1 (fr) * 2015-02-09 2016-08-18 Erwin Reichel Composition sous forme solide pour la lutte contre les incendies
BE1023646B1 (fr) * 2015-11-27 2017-06-01 Uniteq Sa Extincteur a reservoirs pour additifs
CN108245819A (zh) * 2018-01-31 2018-07-06 陈金城 水系灭火剂
US11021608B2 (en) 2018-02-08 2021-06-01 Evonik Operations Gmbh Aqueous polyorganosiloxane hybrid resin dispersion
CN117982822A (zh) * 2022-11-04 2024-05-07 中国石油化工股份有限公司 抑爆剂组合物以及含有残留油品或油气的受限空间的抑爆方法
US12018149B2 (en) 2019-04-01 2024-06-25 Evonik Operations Gmbh Aqueous polyorganosiloxane hybrid resin dispersion
US12091579B2 (en) 2018-12-20 2024-09-17 Evonik Operations Gmbh Universal slip and flow control additives with recoatable quality
US12460081B2 (en) 2021-11-25 2025-11-04 Evonik Operations Gmbh Curable condensation compounds based on alkoxy-functional polysiloxanes
US12473654B2 (en) 2020-08-12 2025-11-18 Evonik Operations Gmbh Use of silicon dioxide for improving the cathodic anticorrosion effect of ground coats

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WO2021087563A1 (fr) * 2019-11-06 2021-05-14 Advanced Wetting Technologies Pty Ltd Composition de mouillage améliorée
ES2837489B2 (es) * 2019-12-31 2022-02-28 Primalchit Solutions S L Mezcla de componentes organicos no polimericos con capacidad retardante de llama, metodo de preparacion y uso

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BE1023646B1 (fr) * 2015-11-27 2017-06-01 Uniteq Sa Extincteur a reservoirs pour additifs
CN108245819A (zh) * 2018-01-31 2018-07-06 陈金城 水系灭火剂
CN108245819B (zh) * 2018-01-31 2020-08-07 陈金城 水系灭火剂
US11021608B2 (en) 2018-02-08 2021-06-01 Evonik Operations Gmbh Aqueous polyorganosiloxane hybrid resin dispersion
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US12018149B2 (en) 2019-04-01 2024-06-25 Evonik Operations Gmbh Aqueous polyorganosiloxane hybrid resin dispersion
US12404407B2 (en) 2019-04-01 2025-09-02 Evonik Operations Gmbh Aqueous polyorganosiloxane hybrid resin dispersion
US12473654B2 (en) 2020-08-12 2025-11-18 Evonik Operations Gmbh Use of silicon dioxide for improving the cathodic anticorrosion effect of ground coats
US12460081B2 (en) 2021-11-25 2025-11-04 Evonik Operations Gmbh Curable condensation compounds based on alkoxy-functional polysiloxanes
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