EP2753403A1 - Mousse d'extinction d'incendie contenant du siloxane - Google Patents

Mousse d'extinction d'incendie contenant du siloxane

Info

Publication number
EP2753403A1
EP2753403A1 EP12753148.1A EP12753148A EP2753403A1 EP 2753403 A1 EP2753403 A1 EP 2753403A1 EP 12753148 A EP12753148 A EP 12753148A EP 2753403 A1 EP2753403 A1 EP 2753403A1
Authority
EP
European Patent Office
Prior art keywords
solution
carbohydrate
acid
spreading
surfactant
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.)
Granted
Application number
EP12753148.1A
Other languages
German (de)
English (en)
Other versions
EP2753403B1 (fr
Inventor
Dirk Blunk
Ralf Helmut HETZER
Angela Sager-Wiedmann
Kai Wirz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Universitaet zu Koeln
Original Assignee
Universitaet zu Koeln
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Universitaet zu Koeln filed Critical Universitaet zu Koeln
Publication of EP2753403A1 publication Critical patent/EP2753403A1/fr
Application granted granted Critical
Publication of EP2753403B1 publication Critical patent/EP2753403B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • A62D1/0071—Foams

Definitions

  • the present invention relates to the field of fire-extinguishing foams or foam concentrates.
  • Fuels are the extinguishing water usually added special foaming agents. These have surfactant properties and allow in contrast to conventional
  • Extinguishing foam means the self-wetting of the burned material surface. 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.
  • the wetting ability characteristic of the AFFF foams also allows the foam to slide on the surface of the burning liquid so that it also reaches areas where the extinguishing foam can not be applied directly.
  • the Schaumfiambae closes after disturbance (for example, by falling objects) again independently.
  • the film also flows and acts in areas that are not directly reached by foam.
  • PFOS perfluorooctyl sulfonate
  • Extinguishing foams with more than 50 ppm PFOS content must not be used in the EU.
  • various other 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-extinguishing foam concentrate which comprises a surfactant containing at least one substituted or unsubstituted carbohydrate or carbohydrate derivative and at least one oligosiloxane.
  • the term "containing" in this context means that both the carbohydrate or carbohydrate derivative and the oligosiloxane are subcomponents of a larger molecule and both are attached via covalent bonds to the remainder of the molecule are suitable and, depending on the application, at least one of the following advantages can be achieved:
  • the total molecular size of the surfactants of the invention is sufficiently small with sufficient solubility; small
  • the surfactant is halogen-free, in particular fluorine-free and can be produced as far as possible from renewable raw materials.
  • the surfactants enable the self-formation of a closed water film on the surface of the fire (eg fuel): As a vapor barrier, this water film impedes the transition of the flammable liquid into the gas phase and thus minimizes the fire that sustains the fire or flammable gas mixtures forms.
  • the surfactant comprises a molecule selected from the group comprising
  • B represents an optional linker substructure of at least one atom or a chain and C is an oligosiloxane, preferably a di-, tri- or tetrasiloxane
  • A is a substituted or unsubstituted carbohydrate or carbohydrate derivative having one to four sugar units.
  • Preferred are mono-, di- and trisaccharides, i. one, two or three sugar units.
  • 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
  • Aldar acids sugar alcohols (alditols), aminosugars or cyclitols, as well as their emerns, 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
  • carbohydrates are substituted, ethyleneoxy, oligo (ethyleneoxy), methyl, ethyl, allyl or acetyl substituents are preferred.
  • preferred carbohydrates or carbohydrate derivatives are monosaccharides: glucose, glucosamine, fructose, galactose for disaccharides: maltose, isomaltose, sucrose, cellobiose, lactose, trehalose in trisaccharides: raffmose, maltotriose, isomaltotriose, maltotriulose, ciceritol in cyclitols: inosite, quebrachitol, pinitol in sugar acids: gluconic acid, glucuronic acid, glucaric acid, tartaric acid, galactonic acid, galacturonic acid, galactaric acid , Mannonic acid, mannuronic acid, mannaric acid, fructonic acid, fructuric acid, arabinonic acid, arabinuronic acid, arabinaric acid, xylonic acid, xyluronic acid, xylaric acid, ribonic acid, riburonic acid, riburonic
  • B is an optional linker substructure of at least one atom or chain, preferably of carbon and / or nitrogen and / or oxygen atoms (O-O bonds being excluded). This chain may be a pure alkyl chain, i. B is an unsubstituted or optionally
  • alkyl-substituted alkylene radical alkyl-substituted alkylene radical
  • B may also contain ether, ester or amide groups.
  • B may contain glycerol, poly- or oligoethylene glycol, poly- or oligopropylene glycol, pentaerythritol, alkylamines or carboxylic acids as a substructure.
  • B is preferably linked to residue A glycosidically via an anomeric carbon atom.
  • B may also be linked to A via an amide or ester bond.
  • residue C the siloxane
  • B is preferably linked via an Si-C or Si-O bond.
  • subcomponent B may also be omitted, i. if necessary, A and C are directly linked.
  • radical B-C or C may also be attached to other regiochemical positions of the carbohydrate or carbohydrate derivative A.
  • Subcomponent C is
  • C 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 may be linked to B (or optionally A) via one of the terminal siloxanes (forming a kind of "continuous chain"), alternatively C may be combined with B (or optionally A ) may also be linked via one of the medium siloxanes, so that a type of X- or T-shaped or branched structure forms.
  • C is derived from a di- or trihydro siloxane
  • the substructures A-B or A joined to C may be the same or different.
  • C has one of the following structures:
  • 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 foam concentrate comprises one or more of the following constituents:
  • Foaming agents Preservatives and corrosion inhibitors, solubilizers and buffers.
  • linear alkylbenzenesulfonates may in particular be: linear alkylbenzenesulfonates, secondary alkanesulfonates, sodium alkylsulfonates, ⁇ -olefinsulfonates, sulfosuccinic acid esters, ⁇ -methyl ester sulfonates, alcohol ethoxylates, alkylphenol ethoxylates, fatty alcohol ethylene oxide / propylene oxide adducts, Glycoside surfactants (eg, glucopone, this is particularly preferred), lauryl sulfates, laureth sulfates, imidazolium salts, lauriminodipropionate, acrylic copolymers.
  • linear alkylbenzenesulfonates may in particular be: linear alkylbenzenesulfonates, secondary alkanesulfonates, sodium alkylsulfonates, ⁇ -olefinsulfonates, sulf
  • 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 foam concentrate may be admixed with, inter alia, the following constituents: polysaccharides, alginates,
  • Temperatures may be admixed with the foaming agent concentrate, 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:
  • Buffer The siloxane surfactants are pH-sensitive in terms of shelf life. A buffering of the concentrate to a pH of about 7 is therefore advantageous. Buffer systems can be for example:
  • Citric acid / sodium acetate Citric acid / sodium acetate.
  • 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 oligosiloxane 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 II relates to a surfactant according to the present invention having the structure:
  • Example III refers to a surfactant according to the present invention having the structure:
  • Example IV relates to a surfactant according to the present invention having the following structure
  • Example V refers to a surfactant according to the present invention having the following
  • Example VI refers to a surfactant according to the present invention having the following
  • Example VII relates to a surfactant according to the present invention having the structure:
  • Example VIII relates to a surfactant according to the present invention having the structure:
  • Example IX relates to a surfactant according to the present invention having the structure:
  • Example X refers to a surfactant according to the present invention having the structure:
  • Example X The spreading behavior of a solution of 2 g / L Example X was investigated; it was found out that this connection is spreading. Similarly, for a solution of 2 g / L, Example X and 0.5 g / L SDS apply.
  • Example XI refers to a surfactant according to the present invention having the structure:
  • surfactants were selected which contain polyethylene glycol units instead of the carbohydrate residues.
  • surfactant I As comparison surfactant I, a surfactant was selected which contains polyethylene glycol moieties instead of the carbohydrate moieties. It has the following structure:
  • Comparative Example II a compound having the following structure was chosen: A solution of 2 g / L Comparative Example II and 0.5 g / L SDS was investigated. The solution collects at the bottom of the dish, no spreading was observed. The same behavior was shown by a solution of Comparative Example II without SDS.
  • siloxane-glycoside surfactants shown in the examples may include i.a. be prepared from the 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)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne des mousses d'extinction d'incendie ou leurs concentrés qui contiennent un tensioactif à base de siloxane contenant des hydrates de carbone.
EP12753148.1A 2011-09-06 2012-09-03 Mousse d'extinction d'incendie contenant du siloxane Active EP2753403B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102011053304A DE102011053304A1 (de) 2011-09-06 2011-09-06 Siloxanhaltiger Feuerlöschschaum
PCT/EP2012/067109 WO2013034521A1 (fr) 2011-09-06 2012-09-03 Mousse d'extinction d'incendie contenant du siloxane

Publications (2)

Publication Number Publication Date
EP2753403A1 true EP2753403A1 (fr) 2014-07-16
EP2753403B1 EP2753403B1 (fr) 2018-11-14

Family

ID=46758780

Family Applications (1)

Application Number Title Priority Date Filing Date
EP12753148.1A Active EP2753403B1 (fr) 2011-09-06 2012-09-03 Mousse d'extinction d'incendie contenant du siloxane

Country Status (9)

Country Link
US (2) US9446272B2 (fr)
EP (1) EP2753403B1 (fr)
JP (1) JP2014526941A (fr)
AU (1) AU2012306469B2 (fr)
CA (1) CA2881929C (fr)
DE (1) DE102011053304A1 (fr)
ES (1) ES2709000T3 (fr)
RU (1) RU2595673C2 (fr)
WO (1) WO2013034521A1 (fr)

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DE102013102239A1 (de) 2013-03-06 2014-09-11 Universität Zu Köln Carbosilanhaltiger Feuerlöschschaum
SG11201608261WA (en) 2014-04-02 2016-10-28 Tyco Fire Products Lp Fire extinguishing compositions and method
DE102014112851A1 (de) * 2014-09-05 2016-03-10 Universität Zu Köln Siliziumhaltige organische Säurederivate als umweltfreundliche AFFF-Löschmittel
CN104607100B (zh) * 2015-01-23 2016-07-06 常熟理工学院 一种糖基改性氟硅表面活性剂及其制备方法
ES2888124T3 (es) 2016-03-18 2021-12-30 Tyco Fire Products Lp Compuestos de poliorganosiloxano como componentes activos en espumas de supresión de incendios libres de flúor
AU2017302283B2 (en) 2016-07-29 2021-06-10 Tyco Fire Products Lp Firefighting foam compositions containing deep eutectic solvents
US11117008B2 (en) 2018-04-24 2021-09-14 The Government Of The United States Of America, As Represented By The Secretary Of The Navy Siloxane and glucoside surfactant formulation for fire-fighting foam applications
AU2020262338A1 (en) * 2019-04-23 2021-12-09 Tyco Fire Products Lp Nonfluorinated agent for liquid vehicle systems
WO2021045609A1 (fr) * 2019-09-06 2021-03-11 Choo Hiow San Composition et procédé d'extinction d'incendie
WO2021230143A1 (fr) * 2020-05-14 2021-11-18 信越化学工業株式会社 Composé d'organosilicium et son procédé de production
CN111991744A (zh) * 2020-08-19 2020-11-27 西南石油大学 一种环保型无氟泡沫灭火剂及其制备方法
US11420083B2 (en) 2021-01-06 2022-08-23 The Government Of The United States Of America, As Represented By The Secretary Of The Navy Zwitterionic and glucoside surfactant formulations for fire-fighting foam applications
US11673010B2 (en) 2021-05-14 2023-06-13 Tyco Fire Products Lp Fire-fighting foam concentrate
US11666791B2 (en) 2021-05-14 2023-06-06 Tyco Fire Products Lp Fire-fighting foam composition
AU2022274674A1 (en) 2021-05-14 2023-11-30 Tyco Fire Products Lp Fire-fighting foam composition
US11497952B1 (en) 2021-05-14 2022-11-15 Tyco Fire Products Lp Fire-fighting foam concentrate
US11673011B2 (en) 2021-05-14 2023-06-13 Tyco Fire Products Lp Firefighting foam composition
EP4337339A1 (fr) 2021-05-14 2024-03-20 Tyco Fire Products LP Composition de mousse de lutte contre l'incendie à base de cellulose micro-fibreuse

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Also Published As

Publication number Publication date
US20160332013A1 (en) 2016-11-17
JP2014526941A (ja) 2014-10-09
EP2753403B1 (fr) 2018-11-14
US20140306141A1 (en) 2014-10-16
US9446272B2 (en) 2016-09-20
CA2881929C (fr) 2019-08-06
ES2709000T3 (es) 2019-04-12
AU2012306469B2 (en) 2016-03-03
AU2012306469A1 (en) 2014-04-03
CA2881929A1 (fr) 2013-03-14
RU2014106757A (ru) 2015-10-20
US9687686B2 (en) 2017-06-27
DE102011053304A1 (de) 2013-03-07
RU2595673C2 (ru) 2016-08-27
WO2013034521A1 (fr) 2013-03-14

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