# US 7,608,208 B2 · Additives for water for fire protection > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 7,608,208 B2 - Document ID: US7608208B2 - Status: Granted - Kind: B2 - Application number: 10/474,522 - Filed: 2002-02-08 - Published: 2004-10-28 - Granted: 2009-10-27 - Earliest claimed: 2001-04-10 - Assignees: Evonik Stockhausen GmbH - Inventors: Jochen Houben; Erich Küster; Martin Tennie - Web page: https://patentgrep.com/patent/US7608208B2 ## CPC - A62D 1/0042: {"Wet" water, i.e. containing surfactant} - A62D: CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS ## Abstract The current invention relates to water-swellable polymers at least partially comprised of sulfonic acid group containing monomers as additives for fire extinguishing water, which exhibits an elevated NaCl content, used in fire prevention and to combat fire. ## Claims ### Claim 1 A method of using water-swellable polymers in fire prevention or fire fighting comprising: (i) adding a salt containing water having common salt (NaCl) as the largest saline moiety and between about 2 and 28 weight-% total salt content and a quantity of an additive comprising a water-swellable polymer at least partially based on at least one sulfonic acid group containing unsaturated monomer to make a fire extinguishing water composition, the water-swellable polymer comprising at least: (a) between about 50 and 70 mol-% of at least one sulfonic acid group containing monomer, (b) between about 10 and 60 mol-% of at least one nonionic monomer selected from any one of methacrylamide, n-alkyl-substituted acrylamide, 2-hydroxyethylacrlate, 2-hydroxyethylmethacrylate, hydroxypropylacrylate, hydroxypropylmethacrylate, C1-C4 alkyl(meth)acrylate, vinyl acetate, acrylamide, or combinations thereof, and (c) between about 0.1 to 3 mol-% of at least one cross-linking agent; and (ii) applying the fire extinguishing water composition to a surface for fire protection or fire fighting, wherein the quantity of the additive used in the fire extinguishing water composition is an amount that provides an amount of electrolyte sufficient to raise a viscosity of the fire extinguishing water composition to over about 1000 mPas. ### Claim 2 (depends on 1) The method according to claim 1, wherein the salt containing water comprises brackish water or sea water. ### Claim 3 (depends on 1) The method according to claim 1, wherein the salt containing water has between about 2 and 10 weight-% total salt content. ### Claim 4 (depends on 3) The method according to claim 3, wherein the salt containing water has between about 2 and 500 total salt content. ### Claim 5 (depends on 1) The method according to claim 1, wherein the at least one sulfonic acid group containing unsaturated monomer is selected from the group consisting of olefinic unsaturated monomers, water-soluble salts of olefinic unsaturated monomers, or combinations thereof. ### Claim 6 (depends on 5) The method according to claim 5, wherein the at least one sulfonic acid group containing unsaturated monomer is selected from the group consisting of aliphatic vinyl sulfonic acids, aromatic vinyl sulfonic acids, water-soluble salts of aliphatic vinyl sulfonic acids, water-soluble salts of aromatic vinyl sulfonic acids, or combinations thereof. ### Claim 7 (depends on 6) The method according to claim 6, wherein the at least one sulfonic acid group containing unsaturated monomer is selected from the group consisting of allyl sulfonic acid, methallyl sulfonic acid, styrene sulfonic acid, acryl sulfonic acid, methacryl sulfonic acid, water-soluble salts of allyl sulfonic acid, water-soluble salts of methallyl sulfonic acid, water-soluble salts of styrene sulfonic acid, water-soluble salts of acryl sulfonic acid, water-soluble salts of methacryl sulfonic acid, or combinations thereof. ### Claim 8 (depends on 7) The method according to claim 7, wherein the at least one sulfonic acid group containing unsaturated monomer is selected from the group consisting of sulfoethylacrylate, sulfoethylmethacrylate, sulfopropylacrylate, sulfopropylmethacrylate, 2-hydroxy-3-methacryloxypropylsulfonic acid, water-soluble salts of sulfoethylacrylate, water-soluble salts of sulfoethylmethacrylate, water-soluble salts of sulfopropylacrylate, water-soluble salts of sulfopropylmethacrylate, water-soluble salts of 2-hydroxy-3-methacryloxypropylsulfonic acid, or combinations thereof. ### Claim 9 (depends on 8) The method according to claim 8, wherein the at least one sulfonic acid group containing unsaturated monomer is selected from the group consisting of 2-acrylamidopropane sulfonic acid, a water-soluble salt of 2-acrylamidopropane sulfonic acid, or combinations thereof. ### Claim 10 (depends on 1) The method according to claim 1, wherein the at least one cross-linking agent is at least a multi-functional cross-linking agent. ### Claim 11 (depends on 1) The method according to claim 1, wherein the at least one cross-linking agent is at least a compound with at least two olefinic unsaturated double bonds. ### Claim 12 (depends on 8) The method according to claim 8, wherein the polymers are cross-linked with a cross-linking agent. ### Claim 13 (depends on 12) The method according to claim 12, wherein the cross-linking agent is at least a multi-functional cross-linking agent. ### Claim 14 (depends on 13) The method according to claim 13, wherein the cross linking agent is at least a compound with at least two olefinic unsaturated double bonds. ### Claim 15 (depends on 1) The method according to claim 1, wherein the at least one residual polymer eradicator is added to the water-swellable polymer after the polymerization. ### Claim 16 (depends on 1) The method according to claim 1, wherein the at least one sulfonic acid group containing monomer comprises several monomers containing sulfonic acid groups. ### Claim 17 (depends on 1) The method according to claim 1, wherein the water-swellable polymer comprises between about 25 and 50 mol-% of at least one nonionic monomer. ### Claim 18 (depends on 1) The method according to claim 1, wherein the water-swellable polymer comprises between about 0.15 and 1 mol-% of at least one cross-linking agent. ### Claim 19 (depends on 1) The method according to claim 1, wherein the water-swellable polymer comprises between about 0.2 and 0.5 mol-% of at least one cross-linking agent. ### Claim 20 (depends on 1) The method according to claim 1, wherein the water-swellable polymer comprises between about 0.25 and 10 weight-% of the fire extinguishing water composition. ### Claim 21 (depends on 20) The method according to claim 20, wherein the water-swellable polymer comprises between about 0.5 and 5 weight-% of the fire extinguishing water composition. ### Claim 22 (depends on 21) The method according to claim 21, wherein the water-swellable polymer comprises between about 1 and 3 weight-% of the fire extinguishing water composition. ### Claim 23 (depends on 1) The method according to claim 1, wherein the water-swellable polymer is present as a water-in-oil polymer dispersion. ### Claim 24 (depends on 23) The method according to claim 23, wherein the water-in-oil polymer dispersion is particles of the water-swellable polymer and a largest diameter of the particles is less than about 10 μm. ### Claim 25 (depends on 24) The method according to claim 24, wherein the largest diameter of the particles is less than about 2 μm. ### Claim 26 (depends on 25) The method according to claim 25, wherein the largest diameter of the particles is less than about 1 μm. ### Claim 27 (depends on 23) The method according to claim 23, wherein the water-swellable polymer has a swelling time of not more than about three minutes. ### Claim 28 (depends on 27) The method according to claim 27, wherein the swelling time is not more than about 30 seconds. ### Claim 29 (depends on 28) The method according to claim 28, wherein the swelling time is not more than about 10 seconds. ### Claim 30 (depends on 1) The method according to claim 1, wherein the water-swellable polymer is present as a water-in-water polymer dispersion. ### Claim 31 (depends on 30) The method according to claim 30, wherein the water-in-water polymer dispersion is particles of the water-swellable polymer and a largest diameter of the particles is less than about 10 μm. ### Claim 32 (depends on 31) The method according to claim 31, wherein the largest diameter of the particles is less than about 2 μm. ### Claim 33 (depends on 32) The method according to claim 32, wherein the largest diameter of the particles is less than about 1 μm. ### Claim 34 (depends on 30) The method according to claim 30, wherein the water-swellable polymer has a swelling time of not more than about three minutes. ### Claim 35 (depends on 34) The method according to claim 34, wherein the swelling time is not more than about 30 seconds. ### Claim 36 (depends on 35) The method according to claim 35, wherein the swelling time is not more than about 10 seconds. ### Claim 37 (depends on 30) The method according to claim 30, wherein the water-in-water polymer dispersion is in a concentration of between about 0.25 and 10 vol.-%. ### Claim 38 (depends on 37) The additive according to claim 37, wherein the water-in-water polymer dispersion is in a concentration of between about 0.5 and 5 vol.-% related to the water mixed with polymer. ### Claim 39 (depends on 38) The additive according to claim 38, wherein the water-in-water polymer dispersion is in a concentration of between about 1 and 3 vol.-%. ### Claim 40 (depends on 1) The method according to claim 1, wherein the water-swellable polymer has a swelling time of not more than about three minutes. ### Claim 41 (depends on 40) The method according to claim 40, wherein the swelling time is not more than about 30 seconds. ### Claim 42 (depends on 1) The method according to claim 1, wherein a quantity of the additive used in the fire extinguishing water composition is an amount that provides an amount of electrolyte sufficient to raise a viscosity of the fire extinguishing water composition to over about 5000 mPas. ### Claim 43 (depends on 42) The method according to claim 42, wherein the quantity of the additive used in the fire extinguishing water composition is an amount that provides an amount of electrolyte sufficient to raise the viscosity of the fire extinguishing water composition to over about 5000 and 50,000 mPas. ### Claim 44 (depends on 1) The method according to claim 1, wherein the additive and the water are continuously added as the fire extinguishing water composition is applied to a surface for fire protection or fire fighting. ### Claim 45 (depends on 1) The method according to claim 1, wherein the additive is provided to the water to make a batch of the fire extinguishing water composition prior to the batch being applied to a surface for fire protection or fire fighting using a discharging device. ### Claim 46 An additive comprising a water-swellable polymer for making a fire extinguishing water based composition using a salt containing water having common salt (NaCl) as the largest saline moiety and between about 2 and 28 weight-% total salt content, the water-swellable polymer comprising: (a) between about 50 and 70 mol-% of at least one unsaturated sulfonic acid group containing monomer; (b) between about 25 and 60 mol-% of at least one nonionic monomer selected from any one of methacrylamide, n-alkyl-substituted acrylamide, 2-hydroxyethylacrlate, 2-hydroxyethyl methacrylate, hydroxypropylacrylate, hydroxypropylmethacrylate, C1-C4 alkyl(meth)acrylate, vinyl acetate, acrylamide, or combinations thereof; and (c) between about 0.1 to 3 mol-% of at least one cross-linking agent. ### Claim 47 (depends on 46) The additive according to claim 46, wherein the water-swellable polymer comprises between about 0.25 and 10 weight-% of the fire extinguishing water composition. ### Claim 48 (depends on 47) The additive according to claim 47, wherein the water-swellable polymer comprises between about 0.5 and 5 weight-% of the fire extinguishing water composition. ### Claim 49 (depends on 48) The additive according to claim 48, wherein the water-swellable polymer comprises between about 1 and 3 weight-% of the fire extinguishing water composition. ### Claim 50 (depends on 46) The additive according to claim 46, wherein the water-swellable polymer is present as a water-in-oil polymer dispersion. ### Claim 51 (depends on 50) The additive according to claim 50, wherein the water-in-oil polymer dispersion is particles of the water-swellable polymer and a largest diameter of the particles is less than about 10 μm. ### Claim 52 (depends on 51) The additive according to claim 51, wherein the largest diameter of the particles is less than about 2 μm. ### Claim 53 (depends on 52) The additive according to claim 52, wherein the largest diameter of the particles is less than about 1 μm. ### Claim 54 (depends on 50) The additive according to claim 50, wherein the swelling time is not more than about 10 seconds. ### Claim 55 (depends on 50) The additive according to claim 50, wherein the water-in-oil polymer dispersion is in a concentration of between about 0.25 and 10 vol.-%. ### Claim 56 (depends on 55) The additive according to claim 55, wherein the water-in-oil polymer dispersion is in a concentration of between about 0.5 and 5 vol.-% related to the water mixed with polymer. ### Claim 57 (depends on 56) The additive according to claim 56, wherein the water-in-oil polymer dispersion is in a concentration of between about 1 and 3 vol.-%. ### Claim 58 (depends on 46) The additive according to claim 46, wherein the water-swellable polymer is present as a water-in-water polymer dispersion. ### Claim 59 (depends on 58) The additive according to claim 58, wherein the water-in-water polymer dispersion is particles of the water-swellable polymer and a largest diameter of the particles is less than about 10 μm. ### Claim 60 (depends on 59) The additive according to claim 59, wherein the largest diameter of the particles is less than about 2 μm. ### Claim 61 (depends on 60) The additive according to claim 60, wherein the largest diameter of the particles is less than about 1 μm. ### Claim 62 (depends on 58) The additive according to claim 58, wherein the swelling time is not more than about 10 seconds. ### Claim 63 (depends on 46) The additive according to claim 46, wherein a quantity of the additive used in the fire extinguishing water composition is an amount that provides an amount of electrolyte sufficient to raise the viscosity of the fire extinguishing water composition to over about 1000 mPas. ### Claim 64 (depends on 63) The additive according to claim 63, wherein the quantity of the additive used in the fire extinguishing water composition is an amount that provides an amount of electrolyte sufficient to raise the viscosity of the fire extinguishing water composition to over about 5000 and 50,000 mPas. ### Claim 65 (depends on 46) The additive according to claim 46, wherein the additive and the water are capable of being continuously added as the fire extinguishing water composition is applied to a surface for fire protection or fire fighting. ### Claim 66 (depends on 46) The additive according to claim 46, wherein the additive is capable of being provided to the water so as to make a batch of the fire extinguishing water composition prior to the batch being applied to a surface for fire protection or fire fighting using a discharging device. ### Claim 67 (depends on 46) The additive according to claim 46, wherein the water-swellable polymer includes at least one residual polymer eradicator. ### Claim 68 A fire extinguishing water based composition for use in fire prevention and fire fighting, the fire extinguishing water composition comprising: (a) a salt containing water having common salt (NaCl) as the largest saline moiety and between about 2 and 28 weight-% total salt content; and (b) a dispersion of an additive comprising a water-swellable polymer, the water-swellable polymer comprising: (i) between about 50 and 70 mol-% of at least one unsaturated sulfonic acid group containing monomer; (ii) between about 25 and 60 mol-% of at least one nonionic monomer selected from any one of methacrylamide, n-alkyl-substituted acrylamide, 2-hydroxyethylacrlate, 2-hydroxyethyl methacrylate, hydroxypropylacrylate, hydroxypropylmethacrylate, C1-C4 alkyl(meth)acrylate, vinyl acetate, acrylamide, or combinations thereof; and (iii) between about 0.1 to 3 mol-% of at least one cross-linking agent, wherein a quantity of the additive used in the fire extinguishing water based composition is an amount that provides an amount of electrolyte sufficient to raise a viscosity of the fire extinguishing water based composition to over about 1000 mPas. ### Claim 69 An additive for making a fire extinguishing water based composition using a salt containing water having common salt (NaCl) as the largest saline moiety and between about 2 and 28 weight-% total salt content, the additive comprising a water-in-oil polymer dispersion comprising: (a) between about 50 and 70 mol-% of at least one unsaturated sulfonic acid group containing unsaturated monomer, wherein the at least one sulfonic acid group containing unsaturated monomer is selected from the group consisting of sulfoethylacrylate, sulfoethylmethacrylate, sulfopropylacrylate, sulfopropylmethacrylate, 2-hydroxy-3-methacryloxypropylsulfonic acid, water-soluble salts of sulfoethylacrylate, water-soluble salts of sulfoethylmethacrylate, water-soluble salts of sulfopropylacrylate, water-soluble salts of sulfopropylmethacrylate, water-soluble salts of 2-hydroxy-3-methacryloxypropylsulfonic acid, and combinations thereof; (b) between about 25 and 60 mol-% of at least one nonionic monomer, wherein the at least one nonionic monomer is selected from the group consisting of methacrylamide, n-alkyl-substituted acrylamide, 2-hydroxyethylacrlate, 2-hydroxyethyl methacrylate, hydroxypropylacrylate, hydroxypropyl methacrylate, C1-C4 alkyl(meth)acrylate, vinyl acetate, acrylamide, and combinations thereof; and (c) between about 0.1 to 3 mol-% of at least one cross-linking agent, wherein the additive comprises a water-swellable polymer having a swelling time in said salt containing water of not more than about 30 seconds.