EP2964343B1 - Mousse d'extinction d'incendie renfermant du carbosilane - Google Patents

Mousse d'extinction d'incendie renfermant du carbosilane Download PDF

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Publication number
EP2964343B1
EP2964343B1 EP14708851.2A EP14708851A EP2964343B1 EP 2964343 B1 EP2964343 B1 EP 2964343B1 EP 14708851 A EP14708851 A EP 14708851A EP 2964343 B1 EP2964343 B1 EP 2964343B1
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independently
fire
acid
carbohydrate
methyl
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EP2964343A1 (fr
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Dirk Blunk
Kai Oliver Wirz
Richard Daniel Matthias MEISENHEIMER
Ralf Helmut HETZER
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BLUNK, DIRK
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Universitaet zu Koeln
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    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
    • A62D1/0071—Foams
    • 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
    • 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

Definitions

  • the present invention relates to the field of fire-extinguishing foams.
  • Fuels are the extinguishing water usually added special foaming agents. These have surface-active properties and, in contrast to conventional extinguishing foams, permit the self-wetting of the surface of the burned material. Therefore, such a so-called AFFF (Aqueous Film Forming Foams) extinguishing foams form as a special feature a film of water on the surface of the burning liquid. The resulting vapor barrier makes it more difficult for the combustible liquid to pass into the gas phase and thus maintain the fire or form ignitable or explosive gas mixtures.
  • AFFF Aqueous Film Forming Foams
  • the wetting ability characteristic of the AFFF foams also allows the foam to slide on the surface of the burning liquid so as to reach areas where the foam can not be applied directly.
  • the foam surface closes after failure (for example, by falling objects) again independently.
  • the film also flows and acts in areas that are not directly reached by foam.
  • PFOS perfluorooctylsulfonate
  • EU Directive 2006/122 / EC of 12.12.2006 Extinguishing foams with more than 50 ppm PFOS content must not be used in the EU.
  • various other perfluorinated or polyfluorinated surfactants are used as substitutes for PFOS in AFFF. These surfactants are heretofore believed to be non-bioactive or at least less bioaccumulating and toxic.
  • a final assessment is still pending and the fundamental problem of persistence of polyfluorinated compounds remains intact.
  • a fire-fighting foam concentrate which comprises a surfactant containing at least one substituted or unsubstituted carbohydrate or carbohydrate derivative and at least one linker substructure and at least one oligosilane or oxacarbosilane.
  • containing in this context means that both the carbohydrate or carbohydrate derivative and the oligosilane are subcomponents of a larger molecule and both are linked via covalent bonds to the remainder of the molecule.
  • Substances for extinguishing foams are among others from the US 2007/134283 . DE 44 37 886 and US 2007/135329 known.
  • A is a substituted or unsubstituted carbohydrate or carbohydrate derivative having one to twenty, preferably one to four sugar units.
  • mono-, di- and trisaccharides i. one, two or three sugar units, alternatively and equally preferred are higher saccharides, especially cyclodextrins.
  • subcomponent A or parts of subcomponent A may also be derived from carbohydrate derivatives such as e.g. the sugar acids (aldonic acids, uronic acids or aldaric acids), sugar alcohols (alditols), aminosugars or cyclitols, and their ethers, esters, amides or thioesters.
  • carbohydrate derivatives such as e.g. the sugar acids (aldonic acids, uronic acids or aldaric acids), sugar alcohols (alditols), aminosugars or cyclitols, and their ethers, esters, amides or thioesters.
  • sugar moieties or “carbohydrate” is understood to mean, in particular, hexoses, pentoses or cyclitols, which (in the presence of di- or higher saccharides) are preferably linked to one another in a glycosidic manner.
  • the carbohydrates may be substituted or unsubstituted, with unsubstituted carbohydrates being preferred because of the resulting higher water solubility.
  • Preferred carbohydrates or carbohydrate derivatives in the context of the present invention are for monosaccharides: glucose, glucosamine, fructose, galactose for disaccharides: maltose, isomaltose, sucrose, cellobiose, lactose, trehalose for trisaccharides: raffinose, maltotriose, isomaltotriose, maltotriulose, ciceritol for cyclitols: inositol, quebrachitol, pinitol in the case of sugar acids: gluconic acid, glucuronic acid, glucaric acid, tartaric acid, galactonic acid, galacturonic acid, maleic acid, mannuronic acid, mannaric acid, fructonic acid, fructuronic acid, fructaric acid, arabinonic acid, arabinuronic acid, arabinaric acid, xylonic acid, xyluronic acid, xylaric acid, rib
  • B is a linker substructure selected from the group consisting of unsubstituted or alkyl-substituted alkylene radicals, propylene bridges, ether groups, ester groups, oligopropylene glycol units and oligoethylene glycol units.
  • This chain may be a pure alkyl chain, i.
  • B is an unsubstituted or optionally alkyl-substituted alkylene radical, preferably having three, four, five, six or seven carbon atoms. Particularly preferred are propylene bridges (i.e., three carbon atoms).
  • B may also contain ether or ester groups. Still alternatively and insofar as preferred, B contains an oligoethylene or oligopropylene glycol unit, preferably with two, three or four units. As attachment to the radical C is preferably an ethylene or propylene unit.
  • B is preferably linked to residue A glycosidically via an anomeric carbon atom.
  • B may also be linked to A via an ester bond.
  • residue C the silane
  • B is linked via an Si-C or Si-O bond.
  • radical B-C or C may also be attached to other regiochemical positions of the carbohydrate or carbohydrate derivative A.
  • the "terminal" silanes are tri (m) ethylsilanes (i.e., they have three methyl and / or ethyl moieties, or two methyl and one ethyl or two ethyl and one methyl moiety (s)).
  • the individual silanes are preferably connected via methylene, ethylene or propylene bridges, particularly preferably methylene units, since these have the amphiphobicity of Do not lower the whole molecule too much.
  • C also comprises siloxane units
  • Si-O-Si bridges are of course present.
  • C is a tri- or higher silane
  • C may be linked to B via one of the terminal silanes (forming a kind of "continuous chain")
  • C may be linked to B via one of the intermediate silanes, so that a kind of X- or T-shaped or branched structure forms.
  • the substructures A-B associated with C may be the same or different.
  • C has one of the following structures: wherein each R, independently of one another, is ethyl or methyl, n (each independently of one another) is 1, 2 or 3, and j, k, m are 1-9, preferably 1, 2 or 3, where 1 ⁇ j + k + m ⁇ 10.
  • each R independently of one another, is ethyl or methyl
  • each X independently of one another (CH 2 ) n or O with n (each independently of one another) is 1, 2 or 3
  • j, k, m is 1-9 1, 2 or 3, wherein 1 ⁇ j + k + m ⁇ 10; such as wherein each R, independently of one another, is ethyl or methyl
  • each X independently of one another (CH 2 ) n or O with n (each independently of one another) is 1, 2 or 3
  • j, k is 1-9, preferably 1, 2 or 3, where 1 ⁇ j + k ⁇ 10.
  • D is an oligosiloxane, preferably a di-, tri- or tetrasiloxane.
  • the methyl and ethyl siloxanes or mixed siloxanes with methyl and ethyl radicals are preferred.
  • C is a tri- or higher siloxane
  • D may be linked to B via one of the terminal siloxanes (forming a kind of "continuous chain"), alternatively D may be linked to B also via one of the intermediate siloxanes such that a kind of X- or T-shaped or branched structure forms.
  • the D-linked substructures A-B may be the same or different.
  • D has one of the following structures: wherein each R, independently of one another, is ethyl or methyl and n is between 0 and 10, preferably between 0 and 5, more preferably 0, 1 or 2.
  • the fire-extinguishing foam concentrate still comprises one or more of the following constituents: Foaming agents, film formers, film stabilizers, antifreeze agents, preservatives and corrosion inhibitors, solubilizers and buffers.
  • linear alkylbenzenesulfonates may in particular be: linear alkylbenzenesulfonates, secondary alkanesulfonates, sodium alkylsulfonates, ⁇ -olefinsulfonates, sulfosuccinic esters, ⁇ -methyl ester sulfonates, alcohol ethoxylates, alkylphenol ethoxylates, fatty alcohol ethylene oxide / propylene oxide adducts, glycoside surfactants (these are particularly preferred, eg glucopone), lauryl sulfates , Laureth sulfates, imidazolium salts, lauriminodipropionate, acrylic copolymers.
  • Suitable counterions for the anionic surfactants present in this list are, in particular, Li + , Na + , K + , NH 4 + , N (C 2 H 5 ) 4 +
  • the foaming agent concentrate may, inter alia, be admixed with the following constituents: polysaccharides, alginates, xanthan gum, starch derivatives
  • the foaming agent concentrate may be admixed with, inter alia, the following components: ethylene glycol, propylene glycol, glycerol, 1-propanol, 2-propanol, urea, inorganic salts
  • the foam concentrate may be admixed inter alia with the following components: Formaldehyde solution, alkylcarboxylic acid salts, ascorbic acid, salicylic acid, tolyltriazoles
  • the foam concentrate may be admixed with, inter alia, the following constituents: Butyl glycol, butyl diglycol, hexylene glycol
  • the present invention also relates to the use of a surfactant containing at least one substituted or unsubstituted carbohydrate or Carbohydrate derivative and at least one oligosilane as an additive to fire-fighting foams and / or concentrates.
  • Example I relates to a surfactant according to the present invention having the structure:
  • Example I Example I / g / l Glucopone / g / l spreading behavior 5.0 12.0 Spread moderately well 4.0 12.0 Spread mediocre 3.0 12.0 Spread slowly 2.0 12.0 Spread slowly 3.0 6.0 Spread moderately well 2.0 6.0 Spread mediocre 1.0 6.0 Spread slowly 0.5 6.0 Spread very slowly
  • Example II relates to a surfactant according to the present invention having the structure:
  • Example III relates to a surfactant according to the present invention having the following structure
  • Example IV relates to a surfactant according to the present invention having the structure:
  • Example V relates to a surfactant according to the present invention having the structure:
  • Example VI refers to a mixture of two surfactants, one according to the present invention, having the following structures:
  • Example VIII relates to a surfactant according to the present invention having the structure:
  • silane glycoside surfactants shown in the examples can be prepared, inter alia, from the corresponding carbohydrates as follows:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Business, Economics & Management (AREA)
  • Emergency Management (AREA)
  • Fire-Extinguishing Compositions (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)

Claims (5)

  1. Concentré de mousse extinctrice comprenant un tensioactif contenant au moins un de carbohydrates substitués ou non substitués ou de dérivés de carbohydrates ainsi qu'au moins un oligosilane, dans lequel le tensioactif comprend une molécule choisie parmi le groupe contenant :
    Figure imgb0034
    Figure imgb0035
     ou leurs mélanges,
    où A est un carbohydrate ou un dérivé carbohydrate, substitué ou non substitué, ayant de 1 à 20 unités de sucre,
    B est une sous-structure de groupe de liaison choisie dans le groupe constitué par les radicaux alkylènes non substitués ou substitués par un alkyle, de ponts propylènes, de groupements éthers, de groupements esters, d'unités oligopropylène glycol, et d'unités oligoéthylène glycol,
    C est un oligosilane ou un oxacarbosilane, et
    D est un oligosiloxane.
  2. Concentré selon la revendication 1, dans lequel C est un di-, tri-, tetra- ou pentasilane.
  3. Concentré selon la revendication 1 ou la revendication 2, dans lequel C est choisi parmi les structures suivantes :
    Figure imgb0036
    Figure imgb0037
     dans lesquelles chaque R est indépendamment un éthyle ou un méthyle, n est indépendamment égal à 1, 2 ou 3, de même que j, k, m valent de 1 à 9 de sorte que 1 ≤ j+k+m ≤ 10 ; de même que
    Figure imgb0038
     dans lesquels chaque R est indépendamment un éthyle ou un méthyle, chaque X est indépendamment (CH2)n ou O avec n indépendamment égal à 1, 2 ou 3, de même que j, k, m valent de 1 à 9 de sorte que 1 ≤ j+k+m ≤ 10 ; de même que
    Figure imgb0039
    Figure imgb0040
     dans lesquelles chaque R est indépendamment un éthyle ou un méthyle, chaque X est indépendamment (CH2)n ou O avec n indépendamment égal à 1, 2 ou 3, de même que j, k valent de 1 à 9 de sorte que 1 ≤ j+k ≤ 10.
  4. Concentré selon l'une quelconque des revendications 1 à 3, dans lequel A est un mono-, di- ou trisaccharide, un acide de sucre, un sucre aminé ou un cyclitol, ou un éther, un ester, une amide ou un thioester de ces composés.
  5. Utilisation d'un tensioactif selon l'une quelconque des revendications 1 à 4 en tant qu'additif de concentré de mousse extinctrice et/ou de mousse extinctrice.
EP14708851.2A 2013-03-06 2014-03-05 Mousse d'extinction d'incendie renfermant du carbosilane Active EP2964343B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102013102239.1A DE102013102239A1 (de) 2013-03-06 2013-03-06 Carbosilanhaltiger Feuerlöschschaum
PCT/EP2014/054287 WO2014135601A1 (fr) 2013-03-06 2014-03-05 Mousse d'extinction d'incendie renfermant du carbosilane

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EP2964343A1 EP2964343A1 (fr) 2016-01-13
EP2964343B1 true EP2964343B1 (fr) 2019-11-13

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EP (1) EP2964343B1 (fr)
JP (1) JP6371316B2 (fr)
AU (1) AU2014224688B2 (fr)
CA (1) CA2901045A1 (fr)
DE (1) DE102013102239A1 (fr)
IL (1) IL241220B (fr)
RU (1) RU2643044C2 (fr)
WO (1) WO2014135601A1 (fr)

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DE102014112851A1 (de) 2014-09-05 2016-03-10 Universität Zu Köln Siliziumhaltige organische Säurederivate als umweltfreundliche AFFF-Löschmittel
DE102016000485B3 (de) * 2016-01-14 2016-10-27 Bundesrepublik Deutschland, vertreten durch das Bundesministerium der Verteidigung, vertreten durch das Bundesamt für Ausrüstung, Informationstechnik und Nutzung der Bundeswehr Verwendung eines Siloxantensids als Zusatz zu einer Öl-Herder-Zusammensetzung
US11771938B2 (en) 2016-07-29 2023-10-03 Tyco Fire Products Lp Firefighting foam compositions containing deep eutectic solvents
WO2018124968A1 (fr) * 2016-12-27 2018-07-05 Agency For Science, Technology And Research Formulation d'extincteur à base d'eau
RU2692259C1 (ru) * 2018-12-29 2019-06-24 Федеральное государственное бюджетное учреждение науки Институт элементоорганических соединений им. А.Н. Несмеянова Российской академии наук (ИНЭОС РАН) Этоксисодержащие линейные поликарбосилансилоксаны и способ их получения
CN114269439A (zh) * 2019-04-23 2022-04-01 泰科消防产品有限合伙公司 用于液体车辆系统的非氟化剂

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Also Published As

Publication number Publication date
EP2964343A1 (fr) 2016-01-13
RU2643044C2 (ru) 2018-01-30
IL241220A0 (en) 2015-11-30
US20160001115A1 (en) 2016-01-07
DE102013102239A1 (de) 2014-09-11
US10307627B2 (en) 2019-06-04
CA2901045A1 (fr) 2014-09-12
JP2016517285A (ja) 2016-06-16
JP6371316B2 (ja) 2018-08-08
AU2014224688A1 (en) 2015-09-03
WO2014135601A1 (fr) 2014-09-12
RU2015136626A (ru) 2017-04-10
AU2014224688B2 (en) 2017-05-25
IL241220B (en) 2019-09-26

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