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EP1888185B1 - Utilisation de dispersions aqueuses de polymeres solubles dans l'eau et/ou pouvant gonfler dans l'eau et procede de lutte contre les incendies - Google Patents

Utilisation de dispersions aqueuses de polymeres solubles dans l'eau et/ou pouvant gonfler dans l'eau et procede de lutte contre les incendies Download PDF

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Publication number
EP1888185B1
EP1888185B1 EP06755234A EP06755234A EP1888185B1 EP 1888185 B1 EP1888185 B1 EP 1888185B1 EP 06755234 A EP06755234 A EP 06755234A EP 06755234 A EP06755234 A EP 06755234A EP 1888185 B1 EP1888185 B1 EP 1888185B1
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Prior art keywords
water
soluble
aqueous
anionic
monomers
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EP1888185A1 (fr
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Antje Ziemer
Pulakesh Mukherjee
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BASF SE
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BASF SE
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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
    • A62D1/0028—Liquid extinguishing substances
    • A62D1/005—Dispersions; Emulsions

Definitions

  • the invention relates to the use of aqueous dispersions of water-soluble and / or water-swellable polymers in extinguishing agents and a method for combating fires with aqueous extinguishing agents which contain at least one polymer.
  • extinguishing agent is known that is applicable both as a dry extinguishing agent and as an extinguishing agent additive in water.
  • the extinguishing agent consists essentially of powdery, hydrogel-forming polymers and at least one material with a high surface area and / or capillary and / or fibrous structure.
  • the extinguishing agents may optionally contain an adhesive to improve the adhesion of the hydrogels to the source of the fire.
  • the invention has for its object to provide for the control of fires that can be extinguished with water, a means available that increases the viscosity of water and / or slows the evaporation of water, but practically does not lead to lump formation, storage stable and easy to handle.
  • the object is achieved according to the invention with the use of aqueous dispersions of water-soluble and / or water-swellable anionic polymers and water-soluble neutralizing agents as an additive to aqueous extinguishing agents.
  • An aqueous extinguishing agent should primarily be understood to mean water which may optionally additionally contain at least one flame retardant, a dye and / or a wetting agent.
  • Suitable flame retardants are, for example, ammonium polyphosphate, polybrominated biphenyls (PBB), polybrominated diphenyl ethers (PBDE), tetrabromobisphenol A (TBBA), chloroparaffins and antimony trioxide, alkali metal silicates and borates, urea mixtures, dicyandiamide and organic phosphates.
  • Suitable wetting agents are all surface-active substances such as ethoxylated alcohols having at least 12 carbon atoms in the molecule, ethoxylated phenols and / or ethoxylated polyols such as glycerol or polyethylene glycols.
  • the preparation of the extinguishing agent can be carried out batchwise by a batch process or continuously.
  • an aqueous dispersion of a water-soluble and / or water-swellable anionic polymer is diluted with water to a polymer concentration of at most 5% by weight and the resulting aqueous solution is adjusted to a pH of at least 5.5 by adding at least one water-soluble neutralizing agent one.
  • the aqueous polymer dispersion is preferably diluted by simultaneously introducing it into the water separately from the addition site of the polymer dispersion with the neutralizing agent and stirring the resulting mixture.
  • the neutralizing agent can also be initially charged in the water used for dilution or dosed after addition of the polymer dispersion.
  • the pH of the aqueous extinguishing agent is preferably in the range of 6 to 13, especially 7 to 12.
  • the polymer concentration of the aqueous extinguishing agent is usually 0.01 to 2.5 wt .-%. It is preferably in the range of 0.1 to 2.0 wt%.
  • This extinguishing agent For example, have a viscosity of at least 1000 mPas up to 100,000 mPas, usually the viscosity of the extinguishing agent is above 3,000 mPas, preferably above 5,000 mPas and in particular above 10,000 mPas.
  • the viscosity data refer to the measurement with a Brookfield R / S Rheometer, spindle V40203T01, at 20 rpm and a temperature of 23 ° C.
  • the aqueous extinguishing agents to be used according to the invention have the advantage over extinguishing agents containing a superabsorber that they can be left for a longer time, even at relatively high temperatures, e.g. 80 ° C - can be stored without a practically measurable viscosity reduction.
  • the extinguishing agents according to the invention are pumpable. They can therefore be used e.g. pumped from a reservoir near a fire and sprayed onto the material to be erased.
  • Another application is to spray the extinguishing agent of the invention from a pressure vessel, which is under a nitrogen pressure of, for example, 10 bar, via a valve on burning material to extinguish the fire.
  • the invention furthermore relates to a method for combating fires with aqueous extinguishing agents which comprise at least one polymer, wherein an aqueous dispersion of water-soluble and / or water-swellable anionic polymers and at least one water-soluble neutralizing agent are each continuously mixed with water in such a way that the Mixture has a polymer content of at most 5 wt .-% and a pH of at least 5.5 and uses them directly for fire fighting.
  • the method for controlling fires with aqueous extinguishing agents which comprise at least one polymer can also be carried out batchwise by using an aqueous mixture for firefighting, obtainable by batch mixing an aqueous dispersion of water-soluble and / or water-swellable anionic polymers and at least one water-soluble neutralizing agent with water, wherein the polymer content of the mixture is at most 5, preferably at most 2.5 wt .-% and the pH is at least 5.5, preferably at least 7.5.
  • Aqueous dispersions of water-soluble and / or water-swellable anionic polymers are known, cf. for example US-A 4,380,600 ; EP-A 183 466 ; US-A 5,605,970 ; WO 97/34933 and DE-A 103 38 828 ,
  • Such dispersions are obtainable, for example, by polymerizing water-soluble anionic monomers from the group of the ethylenically unsaturated C 3 -C 5 -carboxylic acids, vinylsulfonic acid, styrenesulfonic acid, acrylamidomethylpropanesulfonic acid, vinylsulfonic acid and / or their alkali metal or ammonium salts in an aqueous solution which contains at least one other polymer and optionally at least one neutral salt as a stabilizer for the resulting polymer dispersion.
  • aqueous dispersions of water-soluble and / or water-swellable anionic polymers which are obtainable by polymerizing water-soluble anionic monomers in an aqueous solution which is free from neutral salts and as stabilizer at least one other water-soluble polymer from the group of polyethylene glycols, polypropylene glycols, Polyvinyl acetates, polyvinyl alcohols, polyvinylimidazoles, water-soluble starches, thermally, oxidatively or enzymatically degraded starches, cationically or anionically modified starches, maltodextrin and polydiallyldimethylammonium chloride.
  • ethylenically unsaturated, anionic monomers include monoethylenically unsaturated C 3 -C 5 -carboxylic acids, such as acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid, vinylsulfonic acid, styrenesulfonic acid, acrylamidomethylpropanesulfonic acid, vinylphosphonic acid, itaconic acid and / or the alkali metal or ammonium salts of these acids into consideration.
  • Preferred anionic monomers include acrylic acid, methacrylic acid, maleic acid and acrylamido-2-methylpropanesulfonic acid.
  • aqueous dispersions of polymers based on acrylic acid are particularly preferred.
  • the anionic monomers can be polymerized either alone to form homopolymers or else mixed with one another to give copolymers. Examples of these are the homopolymers of acrylic acid or copolymers of acrylic acid with methacrylic acid and / or maleic acid.
  • the polymerization of the anionic monomers can also be carried out in the presence of other ethylenically unsaturated monomers.
  • These monomers may be nonionic or may carry a cationic charge.
  • Examples of such comonomers are acrylamide, methacrylamide; Acrylic acid esters of monohydric alcohols having 1 to 20 carbon atoms, methacrylic acid esters of monohydric alcohols having 1 to 20 carbon atoms, vinyl acetate, vinyl propionate, dialkylaminoethyl (meth) acrylates, dialkylaminopropyl (meth) acrylates, diallyldimethylammonium chloride, N-vinylformamide, vinylimidazole and quaternized vinylimidazole , Basic monomers such as dialkylaminoalkyl (meth) acrylates, for example dimethylaminoethyl acrylate or dimethylaminoethyl methacrylate, can be used in the polymerization both in
  • the comonomers are used in the preparation of the anionic polymers, for example in amounts such that the resulting polymers are water-soluble and have an anionic charge. Based on the total amount of monomers used in the polymerization the amount of nonionic and / or cationic comonomers, for example 0 to 99, preferably 5 to 75 wt .-%.
  • Examples of preferred copolymers are copolymers of from 25 to 90% by weight of acrylic acid and from 75 to 10% by weight of acrylamide. Particular preference is given to homopolymers of acrylic acid which are obtainable by free-radical polymerization of acrylic acid in the absence of other monomers and to copolymers of acrylic acid and / or methacrylic acid which are obtained by copolymerizing acrylic acid and / or methacrylic acid in the presence of pentaerythritol triallyl ether, N, N'-divinylethyleneurea, at least two allyl-containing allyl ethers of sugars such as sucrose, glucose or mannose or triallylamine and mixtures of these compounds can be produced.
  • the polymerization can additionally be carried out in the presence of at least one crosslinker. Copolymers having a higher molecular weight are then obtained than when the anionic monomers are polymerized in the absence of a crosslinking agent. Incorporation of a crosslinker in the polymers also results in reduced solubility of the polymers in water. Depending on the amount of copolymerized crosslinker, the polymers become water-insoluble but are swellable in water. There are fluid transitions between complete solubility of the polymers in water and swelling of the polymers in water. Crosslinked copolymers have a high water absorption capacity due to their swelling capacity in water.
  • Crosslinkers which can be used are all compounds which have at least two ethylenically unsaturated double bonds in the molecule. Such compounds are used, for example, in the preparation of crosslinked polyacrylic acids such as superabsorbent polymers, cf. EP-A 858 478 , Page 4, line 30 to page 5, line 43.
  • crosslinkers are triallylamine, pentaerythritol triallether, methylenebisacrylamide, N, N'-divinylethyleneurea, allyl ethers containing at least two allyl groups or vinyl ethers of polyhydric alcohols having at least two vinyl groups, such as sorbitol, 1, 2-ethanediol, 1,4-butanediol, trimethylolpropane, glycerol, diethylene glycol and of sugars such as sucrose, glucose, mannose, completely hydrated with acrylic acid or methacrylic dihydric alcohols having 2 to 4 carbon atoms such as ethylene glycol dimethacrylate, ethylene glycol diacrylate, butanediol dimethacrylate, butanediol diacrylate, diacrylates or dimethacrylates of polyethylene glycols having molecular weights of 300 to 600, ethoxylated trimethylenepropane triacrylates or ethoxylated trimethylene
  • crosslinking agents are used in the preparation of the anionic dispersions, the amounts of crosslinker used in each case are, for example, 0.0005 to 5.0, preferably 0.001 to 1.0,% by weight, based on the total during the polymerization used monomers.
  • Crosslinkers which are preferably used are pentaerythritol triallyl ether, N, N'-divinylethyleneurea, allyl ethers containing at least two allyl groups of sugars, such as sucrose, glucose or mannose and triallylamine, and also mixtures of these compounds.
  • the polymerization can additionally be carried out in the presence of at least one chain transfer agent.
  • chain transfer agents are compounds containing sulfur in bound form, such as dodecylmercaptan, thiodiglycol, ethylthioethanol, di-n-butylsulfide, di-n-octylsulfide, diphenylsulfide, diisopropyldisulfide, 2-mercaptoethanol, 1,3-mercaptopropanol, 3-mercaptopropan-1 , 2-diol, 1,4-mercaptobutanol, thioglycolic acid, 3-mercaptopropionic acid, mercaptobemic acid, thioacetic acid and thiourea, aldehydes, organic acids such as formic acid, sodium formate or ammonium formate, alcohols such as in particular isopropanol and phosphorus compounds,
  • the chain transfer agents are preferably used together with at least one crosslinker in the polymerization. By varying the amount and the ratio of chain transfer agent and crosslinker, it is possible to control the rheology of the resulting polymers. Chain transfer agents and / or crosslinkers may be initially charged in the polymerization, for example, in the aqueous polymerization medium or dosed together or separately from the monomers, depending on the progress of the polymerization, to the polymerization batch.
  • the polymerization usually uses initiators which form radicals under the reaction conditions.
  • Suitable polymerization initiators are, for example, peroxides, hydroperoxides, hydrogen peroxide, sodium or potassium persulfate, redox catalysts and azo compounds such as 2,2-azobis (N, N-dimethyleneisobutyramidine) dihydrochloride, 2,2-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2-azobis (2,4-dimethylvaleronitrile) and 2,2-azobis (2-amidinopropane) dihydrochloride).
  • the initiators are used in the amounts customary in the polymerization.
  • Azo starters are preferably used as polymerization initiators. However, it is also possible to initiate the polymerization by means of high-energy rays such as electron beams or by irradiation with UV light.
  • the aqueous dispersions of the water-soluble anionic polymers have a polymer concentration of anionic polymers of, for example, 1 to 70 wt .-%, usually 5 to 50, preferably 10 to 25 and particularly preferably 15 to 20 wt .-%. They contain at least two different groups of the above-mentioned polymers (A) and (b) for stabilizing the anionic polymers formed in the polymerization.
  • the amount of stabilizers (a) and (b) in the aqueous dispersion is for example 1 to 40 wt .-%, usually 5 to 30 wt .-% and preferably 10 to 25 wt .-%.
  • the aqueous dispersions have, for example at a pH of 2.5, viscosities in the range of 200 to 100,000 mPas, preferably 200 to 20,000 mPas, preferably 200 to 10,000 mPas (measured in a Brookfield viscometer at 20 ° C, Spindle 6, 100 rpm).
  • the stabilizers of group (a) include graft polymers of vinyl acetate and / or vinyl propionate on (i) polyethylene glycols or (ii) on one or both sides with alkyl, carboxyl or amino end-capped polyethylene glycols or polypropylene glycols, and also polyalkylene glycols and one or both sides with alkyl, carboxyl or amino groups end-capped polyalkylene glycols.
  • Polyalkylene glycols are used for example in the WO 03/046024 , Page 4, line 37 to page 8, line 9 described.
  • the polyalkylene glycols described therein can either be used directly as a stabilizer of group (a) or modified to grafted onto 100 parts by weight of the polyalkylene glycols, for example 10 to 1000, preferably 30 to 300 parts by weight of vinyl acetate and / or vinyl propionate.
  • Polyethylene glycol having a molecular weight M N of 1000 to 100 000 is preferably used as the grafting base, and vinyl acetate is grafted thereon.
  • Further suitable stabilizers (a) are the abovementioned polyalkylene glycols and the polyalkylene glycols which are end-capped on one or both sides with alkyl, carboxyl or amino groups.
  • the abovementioned polymers have for example molar masses M N of from 100 to 100,000, preferably from 300 to 80,000, particularly preferably from 600 to 50,000 and in particular from 1,000 to 50,000. Such polymers are described, for example, in the above-cited WO 03/046024 , Page 4, line 37 to page 8, line 9 described.
  • Preferred polyalkylene glycols are, for example, polyethylene glycol, polypropylene glycol and block copolymers of ethylene oxide and propylene oxide.
  • the block copolymers may contain copolymerized ethylene oxide and propylene oxide in any desired amounts and in any order.
  • the OH end groups of the polyalkylene glycols may optionally be end-capped on one or both sides with alkyl, carboxyl or amino groups, with the end group preferably being a methyl group.
  • Particularly preferably used stabilizers of group (a) are copolymers of ethylene oxide and propylene oxide. Particularly preferred are block copolymers of ethylene oxide and propylene oxide having a molecular weight M N of 500 to 20,000 g / mol and a content of ethylene oxide units of 10 to 80 mol%.
  • water-soluble nonionic monomers (b1) are acrylamide, methacrylamide, N-vinylformamide, N-vinylpyrrolidone and N-vinylcaprolactam.
  • all nonionic, monoethylenically unsaturated monomers which have a water solubility of at least 100 g / l at a temperature of 20 ° C. are suitable as monomers of group (b1).
  • Particularly preferred are monomers (b1) which are miscible with water in any ratio and form clear aqueous solutions such as acrylamide or N-vinyl-formamide.
  • Water-soluble, cationic, monoethylenically unsaturated monomers (b2) are, for example, dialkylaminoalkyl (meth) acrlylates such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, diethylaminopropyl acrylate and diethylaminopropyl methacrylate, dialkyldiallyammonium halides such as dimethyldiallylammonium chloride and diethyldiallylammonium chloride, N-vinylimidazole and quaternized N-vinylimidazole.
  • dialkylaminoalkyl (meth) acrlylates such as dimethylaminoethyl acrylate,
  • Basic monomers such as dimethylaminoethyl acrylate or dimethylaminoethyl methacrylate can be used both in the form of the free bases and in partially or completely neutralized form with acids such as hydrochloric acid, sulfuric acid, formic acid and p-toluenesulfonic acid.
  • the basic monomers may also be partially or completely quaternized with C 1 - to C 18 -alkyl halides and / or C 1 - to C 18 -alkyl C 1 - to C 18 -alkylaryl halides and used in this form in the polymerization.
  • dimethylaminoethyl (meth) acrylates quaternized completely with methyl chloride such as dimethylaminoethyl acrylate methochloride or dimethylaminoethyl methacrylate methochloride.
  • the polymers of group (b) may also contain vinylamine units as a cationic group.
  • Such polymers are obtainable, for example, by using N-vinylformamide optionally polymerized together with at least one anionic water-soluble monomer and the polymers are then hydrolyzed with partial elimination of formyl groups to polymers containing vinylamine units.
  • the polymers of group (b) may optionally contain at least one anionic monoethylenically unsaturated monomer (b3) in copolymerized form.
  • anionic monomers which form water-soluble polymers such as acrylic acid, methacrylic acid, vinylsulfonic acid, vinyl-phosphonic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid and the alkali metal and ammonium salts of these acids.
  • polymers (b) are copolymers of acrylamide and dimethylaminoethyl acrylate methochloride, copolymers of acrylamide and dimethylaminoethyl methacrylate metrochloride; Copolymers of acrylamide and dimethylaminopropyl acrylate methochloride, copolymers of methacrylamide and dimethylaminoethyl methacrylmethochloride, Copolymers of acrylamide, Dimethylaminoethylacrylatmethochlorid and acrylic acid, copolymers of acrylamide, Dimethylaminoethylmethacrylatmethochlorid and methacrylic acid and copolymers of acrylamide, Dimethylaminoethylacrylatmethochlorid and acrylic acid.
  • the polymers (b) have for example a K value of 15 to 200, preferably 30 to 150 and particularly preferably 45 to 110 (determined according to H. Fikentscher, Cellulose Chemistry, Vol. 13, 58-64 and 71-74 (1932 in 3% by weight aqueous cooking oil solution at 25 ° C, a polymer concentration of 0.1% by weight and a pH of 7).
  • the average molecular weight of the anionic polymers which are suitable as component (b) of the stabilizer mixture is, for example, up to 1.5 million, usually up to 1 million, and is preferably in the range from 1000 to 100,000 (determined by the method of light scattering).
  • the aqueous dispersions contain the polymers of group (b), for example, in amounts of 0.5 to 15, preferably 1 to 10 wt .-%.
  • the copolymer (b) may optionally contain up to 5 mol% of acrylic acid in copolymerized form.
  • component (b) of stabilizer mixtures for the preparation of aqueous dispersions of water-soluble anionic polymers are in particular also hydrolyzed copolymers of vinyl alkyl ethers and maleic anhydride and the resulting from partial or complete neutralization with alkali metal and / or ammonium bases available salts of the copolymers into consideration.
  • the alkyl group of the vinyl alkyl ethers may have, for example, 1 to 4 carbon atoms.
  • the copolymers are obtainable by copolymerizing vinyl alkyl ethers with maleic anhydride and subsequent hydrolysis of the anhydride groups to carboxyl groups and optionally partial or complete neutralization of the carboxyl groups.
  • Particularly preferred water-soluble polymers of group (b) are hydrolyzed copolymers of vinyl methyl ether and maleic anhydride in the form of the free carboxyl groups and in the form of at least partially neutralized with sodium hydroxide, potassium hydroxide or ammonia salts.
  • water-soluble polymers of group (b) are water-soluble starches from the group of cationically modified potato starch, anionically modified potato starch, degraded potato starch and maltodextrin.
  • cationically modified potato starches are the commercial products Amylofax 15 and Perlbond 970.
  • a suitable anionically modified potato starch is Perfectamyl A 4692. Here the modification consists essentially in a carboxylation of potato starch.
  • C * Pur 1906 is an example of an enzymatically degraded potato starch and maltodextrin C 01915 for a hydrolytically degraded potato starch. Of the mentioned starches, maltodextrin is preferably used.
  • preferably used polymers of component (b) of the stabilizer mixtures are homopolymers and copolymers having molecular weights M w up to 100 000 of anionic monomers, for example homopolymers of ethylenically unsaturated C 3 - to C 5 -carboxylic acids such as in particular homopolymers of acrylic acid or methacrylic acid, or other acid group-containing monomers such as acrylamidomethylpropanesulfonic acid, styrenesulfonic acid, sulfoethyl acrylate, sulfoethyl methacrylate, vinylsulfonic acid and vinylphosphonic acid and the alkali metal and ammonium salts of the acid group-containing monomers.
  • anionic monomers for example homopolymers of ethylenically unsaturated C 3 - to C 5 -carboxylic acids such as in particular homopolymers of acrylic acid or methacrylic acid, or other acid group-containing monomers such as
  • the said anionic monomers may be partially or completely neutralized.
  • copolymers of anionic monomers for example copolymers of acrylic acid and methacrylic acid, copolymers of acrylic acid and maleic acid, copolymers of methacrylic acid and maleic acid, and copolymers of acrylic acid and itaconic acid.
  • suitable polymers which are used as component (b) of the stabilizer mixtures are copolymers of (i) anionic and (ii) cationic and optionally (iii) neutral monomers, the proportion of copolymerized anionic monomers being greater than that of the cationic monomers.
  • anionic monomers the monomers mentioned in the preceding paragraph can be used. Particularly preferred are acrylic acid, methacrylic acid, maleic acid and acrylamidomethylpropanesulfonic acid.
  • cationic monomers are water-soluble, cationic, monoethylenically unsaturated monomers which are already mentioned above in the case of the stabilizers (b) under (b2) which carry a cationic charge, for example dialkylaminoalkyl (meth) acrlylates in the form of the salts with acids or in quaternized form, dialkyldiallyammonium halides such as dimethyldiallylammonium chloride and diethyldiallylammonium chloride, quaternized N-vinylimidazole.
  • dialkylaminoalkyl (meth) acrlylates in the form of the salts with acids or in quaternized form dialkyldiallyammonium halides such as dimethyldiallylammonium chloride and diethyldiallylammonium chloride, quaternized N-vinylimidazole.
  • Examples of (iii) neutral monomers are all esters of monohydric C 1 to C 18 monohydric alcohols, styrene, N-vinylpryrrolidone, N-vinylimidazole, N-vinylformamide, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, vinyl acetate and vinyl propionate.
  • component (b) of stabilizer mixtures polymers are copolymers of (i) at least one anionic monomer (such monomers are already exemplified above) and (ii) at least one neutral monomer selected from the group of esters of anionic monomers with monohydric alcohols, styrene , N-vinylpryrrolidone, N-vinylimidazole, N-vinylformamide, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, vinyl acetate and vinyl propionate.
  • Particularly preferred from this group (b) are copolymers of acrylic acid and methyl acrylate and copolymers of acrylic acid, acrylamidomethylpropanesulfonic acid, methyl acrylate and styrene.
  • the molecular weights M w of the abovementioned polymers are, for example, in the range from 1,000 to 100,000, preferably 1,500 to 70,000 and usually 2,000 to 30,000 (determined by light scattering).
  • the ratio of components (a) and (b) in the stabilizer mixtures can be varied within a wide range. For example, it can be 50: 1 to 1:10. It is preferable to choose a ratio of (a) :( b) of at least 1.5: 1, in particular from 7: 1 to 10: 1.
  • the stable aqueous dispersions of water-soluble anionic polymers obtainable in this way have, for example, a particle size of 0.1 to 200 .mu.m, preferably 0.5 to 70 .mu.m.
  • the particle size can be z. As determined by optical microscopy, light scattering or freeze-fracture electron microscopy.
  • the aqueous dispersions are prepared, for example, at pH values of 0.5 to 5, preferably 1 to 3. At pH values below 5, dispersions containing about 5 to 35% by weight of anionic polymers have a relatively low viscosity.
  • the aqueous polymer dispersion is used together with at least one neutralizing agent.
  • neutralizing agents are, for example, an alkali metal, alkaline earth metal and / or ammonium base Consideration.
  • neutralizing agents are sodium hydroxide solution, potassium hydroxide solution, ammonia, ethanolamine, diethanolamine or triethanolamine.
  • all other amines or polyamines such as diethylenetriamine, triethylenetetramine, polyethyleneimines and / or polyvinylamines can be used as neutralizing agent.
  • a preferred embodiment of the invention consists of continuously mixing with water an aqueous dispersion of water-soluble and / or water-swellable anionic polymers and at least one water-soluble neutralizing agent such that the mixture, i.
  • aqueous dispersions of anionic polymers which are crosslinked are crosslinked.
  • the crosslinking agent is most often used during the polymerization to give polymer particles that are cross-linked throughout.
  • the emulsions give in the application according to the invention clear gels, which are storage stable even at higher temperatures. They are liable to fire fighting on vertical surfaces and effectively hinder too fast evaporation of the fire-fighting water. They are particularly suitable in extinguishing water, which is discharged from a greater height to a fire, e.g. from a helicopter.
  • the viscosities reported in the examples were measured in a Brookfield R / S Rheometer, spindle V 40203T01, at 20 rpm and a temperature of 23 ° C.
  • the parts mean parts by weight.
  • azo starter VA 044 [2,2'-azobis (N, N'-dimethyleneisobutyramidine) dihydrochloride] in 10 g of completely demineralized water was added and rinsed with 10 g of water. The reaction mixture was then heated to a temperature of 40 ° C with continuous passage of nitrogen and polymerized at this temperature for 5 hours. Thereafter, 0.3 g of azo starter VA 044 in 10 g of completely deionized water was added, rinsed with 10 g of completely deionized water and the reaction mixture was stirred for 2 hours at 40 ° C for postpolymerization. This gave a white emulsion which had a viscosity of 1200 mPas. It will be referred to below as Dispersion A.

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Claims (16)

  1. Utilisation de dispersions aqueuses de polymères anioniques solubles dans l'eau et/ou gonflables dans l'eau et d'agents de neutralisation solubles dans l'eau en tant qu'additif pour des extincteurs aqueux.
  2. Utilisation selon la revendication 1, caractérisée en ce qu'une dispersion aqueuse de polymères anioniques solubles dans l'eau et/ou gonflables dans l'eau est diluée avec de l'eau à une concentration de polymères inférieure ou égale à 5 % en poids et ajustée à un pH supérieur ou égal à 5,5 avec au moins un agent de neutralisation soluble dans l'eau.
  3. Utilisation selon la revendication 1 ou 2, caractérisée en ce que le pH de l'extincteur aqueux est de 6 à 13.
  4. Utilisation selon l'une quelconque des revendications 1 à 3, caractérisée en ce que le pH de l'extincteur aqueux est de 7 à 12.
  5. Utilisation selon l'une quelconque des revendications 1 à 4, caractérisée en ce que la concentration en polymères de l'extincteur aqueux est de 0,01 à 2,5 % en poids.
  6. Utilisation selon l'une quelconque des revendications 1 à 5, caractérisée en ce que la concentration en polymères de l'extincteur aqueux est de 0,1 à 2,0 % en poids.
  7. Utilisation selon l'une quelconque des revendications 1 à 6, caractérisée en ce que l'on utilise des dispersions aqueuses de polymères anioniques solubles dans l'eau et/ou gonflables dans l'eau qui peuvent être obtenus par polymérisation de monomères anioniques solubles dans l'eau du groupe des acides carboxyliques en C3 à C5 à insaturation éthylénique, de l'acide vinylsulfonique, de l'acide styrènesulfonique, de l'acide acrylamidométhylpropanesulfonique et/ou leurs sels de métaux alcalins ou d'ammonium dans une solution aqueuse qui contient au moins un autre polymère et éventuellement au moins un sel neutre en tant que stabilisateur pour la dispersion polymère formée.
  8. Utilisation selon l'une quelconque des revendications 1 à 6, caractérisée en ce que l'on utilise des dispersions aqueuses de polymères anioniques solubles dans l'eau et/ou gonflables dans l'eau qui peuvent être obtenus par polymérisation de monomères anioniques solubles dans l'eau dans une solution aqueuse qui ne contient pas de sels neutres et qui contient en tant que stabilisateur au moins un autre polymère soluble dans l'eau du groupe des polyéthylène glycols, polypropylène glycols, acétates de polyvinyle, alcools polyvinyliques, polyvinylimidazoles, amidons solubles dans l'eau, amidons décomposés thermiquement, oxydativement ou enzymatiquement, amidons modifiés cationiquement ou anioniquement, maltodextrine et chlorure de polydiallyldiméthylammonium.
  9. Utilisation selon l'une quelconque des revendications 1 à 6, caractérisée en ce que l'on utilise des polymères anioniques solubles dans l'eau et/ou gonflables dans l'eau qui peuvent être obtenus par polymérisation de monomères anioniques solubles dans l'eau dans une solution aqueuse qui ne contient pas de sels neutres et qui contient en tant que stabilisateur au moins un polymère soluble dans l'eau des groupes
    (a) polymères greffés d'acétate de vinyle et/ou de propionate de vinyle sur des polyéthylène glycols, polyéthylène glycols comportant d'un ou des deux côtés des groupements terminaux alkyle, carboxyle ou amino, copolymères d'acrylates d'alkylpolyalkylène glycol ou de méthacrylates d'alkylpolyalkylène glycol et d'acide acrylique et/ou d'acide méthacrylique, polyalkylène glycols avec des masses molaires MN de 1 000 à 100 000, polyalkylène glycols comportant d'un ou des deux côtés des groupements terminaux alkyle, carboxyle ou amino ayant des masses molaires MN de 1 000 à 100 000
    et
    (b) copolymères hydrolysés d'éthers de vinyle alkyle et d'anhydride d'acide maléique sous la forme des groupements carboxyles libres et sous la forme des sels au moins partiellement neutralisés avec des hydroxydes de métaux alcalins ou des bases d'ammonium et/ou un amidon soluble dans l'eau du groupe de l'amidon de pomme de terre modifié cationiquement, de l'amidon de pomme de terre modifié anioniquement, de l'amidon de pomme de terre décomposé et de la maltodextrine.
  10. Utilisation selon l'une quelconque des revendications 1 à 6, caractérisée en ce que l'on utilise des dispersions aqueuses de polymères anioniques solubles dans l'eau et/ou gonflables dans l'eau qui peuvent être obtenus par polymérisation de monomères anioniques solubles dans l'eau dans une solution aqueuse qui ne contient pas de sels neutres et qui contient en tant que stabilisateur au moins un polymère soluble dans l'eau des groupes
    (a) polymères greffés d'acétate de vinyle et/ou de propionate de vinyle sur (i) des polyéthylène glycols ou (ii) des polyéthylène glycols ou des polypropylène glycols comportant d'un ou des deux côtés des groupements terminaux alkyle, carboxyle ou amino, des polyalkylène glycols, des polyalkylène glycols comportant d'un ou des deux côtés des groupements terminaux alkyle, carboxyle ou amino
    et
    (b) des copolymères solubles dans l'eau de
    (b1) monomères non ioniques à insaturation monoéthylénique,
    (b2) monomères cationiques à insaturation monoéthylénique et éventuellement
    (b3) monomères anioniques à insaturation monoéthylénique, la proportion de monomères cationiques incorporés par polymérisation étant supérieure à celle de monomères anioniques.
  11. Utilisation selon l'une quelconque des revendications 1 à 6, caractérisée en ce que l'on utilise des dispersions aqueuses de polymères anioniques solubles dans l'eau et/ou gonflables dans l'eau qui peuvent être obtenus par polymérisation de monomères anioniques solubles dans l'eau dans une solution aqueuse qui ne contient pas de sels neutres et qui contient en tant que stabilisateur au moins un polymère soluble dans l'eau des groupes
    (a) polymères greffés d'acétate de vinyle et/ou de propionate de vinyle sur (i) des polyéthylène glycols ou (ii) des polyéthylène glycols ou des polypropylène glycols comportant d'un ou des deux côtés des groupements terminaux alkyle, carboxyle ou amino, des polyalkylène glycols, des polyalkylène glycols comportant d'un ou des deux côtés des groupements terminaux alkyle, carboxyle ou amino
    et
    (b)
    (i) des homo et copolymères de monomères anioniques,
    (ii) des copolymères de monomères anioniques et cationiques et éventuellement neutres, la proportion de monomères anioniques incorporés par polymérisation étant supérieure à celle de monomères cationiques et
    (iii) des copolymères d'au moins un monomère anionique et d'au moins un monomère du groupe des esters de monomères anioniques avec des alcools monovalentes, du styrène, de la N-vinylpyrrolidone, du N-vinylcaprolactame, du N-vinylimidazol, du N-vinylformamide, de l'acrylamide, du méthacrylamide, de l'acétate de vinyle et du propionate de vinyle.
  12. Utilisation selon l'une quelconque des revendications 1 à 11, caractérisée en ce qu'au moins une base de métal alcalin, de métal alcalino-terreux ou d'ammonium est utilisée en tant qu'agent de neutralisation.
  13. Utilisation selon l'une quelconque des revendications 1 à 12, caractérisée en ce que de la soude caustique, de l'hydroxyde de potassium, de l'ammoniac, de l'éthanolamine, de la diéthanolamine ou de la triéthanolamine est utilisée en tant qu'agent de neutralisation.
  14. Utilisation selon l'une quelconque des revendications 1 à 13, caractérisée en ce que l'extincteur aqueux contient également au moins un agent ignifuge, un colorant et/ou un agent de réticulation.
  15. Utilisation selon l'une quelconque des revendications 1 à 14, caractérisée en ce qu'une dispersion aqueuse de polymères anioniques solubles dans l'eau et/ou gonflables dans l'eau et d'au moins un agent de neutralisation soluble dans l'eau est mélangée avec de l'eau respectivement de manière continue de manière à ce que le mélange présente une teneur en polymères inférieure ou égale à 5 % en poids et un pH supérieur ou égal à 5,5 et une viscosité inférieure ou égale à 100 000 mPas (viscosimètre de Brookfield, fuseau V40203T01, 20 trs/min 23 °C).
  16. Procédé de lutte contre les incendies avec des extincteurs aqueux qui contiennent au moins un polymères, caractérisé en ce qu'une dispersion aqueuse de polymères anioniques solubles dans l'eau et/ou gonflables dans l'eau et d'au moins un agent de neutralisation soluble dans l'eau est mélangée avec de l'eau respectivement de manière continue ou discontinue de manière à ce que le mélange présente une teneur en polymères inférieure ou égale à 5 % en poids et un pH supérieur ou égal à 5,5 et à ce qu'elle puisse immédiatement être utilisée pour lutter contre les incendies.
EP06755234A 2005-05-19 2006-05-17 Utilisation de dispersions aqueuses de polymeres solubles dans l'eau et/ou pouvant gonfler dans l'eau et procede de lutte contre les incendies Not-in-force EP1888185B1 (fr)

Priority Applications (1)

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PL06755234T PL1888185T3 (pl) 2005-05-19 2006-05-17 Zastosowanie wodnych dyspersji polimerów rozpuszczalnych w wodzie i/lub pęczniejących w wodzie w środkach gaśniczych i sposób zwalczania pożarów

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DE102005023800A DE102005023800A1 (de) 2005-05-19 2005-05-19 Verwendung von wässrigen Dispersionen von wasserlöslichen und/oder in Wasser quellbaren Polymeren in Löschmitteln und Verfahren zur Bekämpfung von Bränden
PCT/EP2006/062378 WO2006122946A1 (fr) 2005-05-19 2006-05-17 Utilisation de dispersions aqueuses de polymeres solubles dans l'eau et/ou pouvant gonfler dans l'eau et procede de lutte contre les incendies

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CA (1) CA2608529A1 (fr)
DE (2) DE102005023800A1 (fr)
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Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010142568A1 (fr) * 2009-06-08 2010-12-16 Basf Se Procédé de production d'un tissu non tissé gonflant
US8192653B2 (en) 2009-09-30 2012-06-05 EarthCleanCorporation Fire suppression biodegradable suspension forming compositions
CN102711928B (zh) 2009-10-30 2015-07-01 Fln消防用具诺伊鲁平分部有限公司 适用于制备泡沫灭火剂的组合物
DE102010001741A1 (de) * 2010-02-10 2011-08-11 SB LiMotive Company Ltd., Kyonggi Löschmittel
US8961838B2 (en) 2010-04-05 2015-02-24 Earthclean Corporation Non-aqueous fire suppressing liquid concentrate
WO2012094695A1 (fr) * 2011-01-13 2012-07-19 Biocentral Laboratories Limited Additif pour eau anti-incendie
DE102011003877A1 (de) * 2011-02-09 2012-08-09 Sb Limotive Company Ltd. Zusammensetzung zum Löschen und/oder Hemmen von Fluor- und/oder Phosphor-haltigen Bränden
DE102011003882A1 (de) * 2011-02-09 2012-08-09 Sb Limotive Company Ltd. Zusammensetzung zum Löschen und/oder Hemmen von Fluor- und/oder Phosphor-haltigen Bränden
US20140235790A1 (en) * 2011-06-10 2014-08-21 University Of Washington Through Its Center For Commercialization Carbohydrate-based compositions and methods for targeted drug delivery
US20140202720A1 (en) * 2013-01-22 2014-07-24 GelTech Solutions, Inc. Method and Device for Suppressing Electrical Fires in Underground Conduit
US9993672B2 (en) * 2013-01-22 2018-06-12 GelTech Solutions, Inc. Method and device for suppressing electrical fires in underground conduit
AU2013206711A1 (en) * 2013-07-05 2015-01-22 Biocentral Laboratories Limited Fire Fighting Water Additive
US11110311B2 (en) 2017-05-31 2021-09-07 Tyco Fire Products Lp Antifreeze formulation and sprinkler systems comprising improved antifreezes
CN110947149A (zh) * 2019-12-09 2020-04-03 江苏三安消防设备有限公司 一种改性高分子水系灭火剂及其制备方法
CN115317843B (zh) * 2022-08-31 2024-01-19 四川省林业科学研究院 用于森林防火的灭火剂及其制备方法

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3229769A (en) * 1963-01-28 1966-01-18 Dow Chemical Co Method for controlling the spread of fire
US3976580A (en) * 1975-11-07 1976-08-24 Bernard Kaminstein Gelled fire extinguisher fluid comprising polyacrylamide and bentonite
JPS55721A (en) * 1978-06-19 1980-01-07 Showa Denko Kk Aqueous dispersion of water-soluble high polymer complex
CA1267483A (fr) * 1984-11-19 1990-04-03 Hisao Takeda Production d'un melange de polymere soluble a l'eau
US5190110A (en) * 1985-05-03 1993-03-02 Bluecher Hubert Use of an aqueous swollen macromolecule-containing system as water for fire fighting
DE3603392A1 (de) * 1986-02-05 1987-08-06 Basf Ag Verfahren zur herstellung von polymerisaten der acrylsaeure oder methacrylsaeure
US5849210A (en) * 1995-09-11 1998-12-15 Pascente; Joseph E. Method of preventing combustion by applying an aqueous superabsorbent polymer composition
US5605970A (en) * 1996-03-20 1997-02-25 Nalco Chemical Company Synthesis of high molecular weight anionic dispersion polymers
US6386293B1 (en) * 2000-05-09 2002-05-14 John B. Bartlett Fire combating system and method
AU2004262863B2 (en) * 2003-07-23 2009-06-04 Basf Se Fire control composition and method
DE10338828A1 (de) * 2003-08-21 2005-03-24 Basf Ag Wässrige Dispersionen von wasserlöslichen Polymerisaten von ethylenisch ungesättigten anionischen Monomeren, Verfahren zu ihrer Herstellung und ihre Verwendung
MXPA06000487A (es) * 2003-07-25 2006-04-05 Basf Ag Dispersiones acuosas de polimerizados hidrosolubles de monomeros anionicos etilenicamente insaturados, metodo para la produccion y uso de los mismos.

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AU2006248958B2 (en) 2011-03-10
ES2314920T3 (es) 2009-03-16
US20080185553A1 (en) 2008-08-07
WO2006122946A1 (fr) 2006-11-23
AU2006248958A1 (en) 2006-11-23
PL1888185T3 (pl) 2009-04-30
CA2608529A1 (fr) 2006-11-23
EP1888185A1 (fr) 2008-02-20
DE102005023800A1 (de) 2006-11-23
PT1888185E (pt) 2008-12-12
DE502006001946D1 (de) 2008-12-11
ATE412456T1 (de) 2008-11-15

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