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EP-4377404-B1 - FLUORINE FREE SURFACTANTS AND FOAM COMPOSITIONS

EP4377404B1EP 4377404 B1EP4377404 B1EP 4377404B1EP-4377404-B1

Inventors

  • KASOWSKI, ROBERT VALENTINE
  • SEMINARA, Hahnah, Kasowski

Dates

Publication Date
20260506
Application Date
20220727

Claims (12)

  1. A surfactant solution, wherein the surfactant solution is formed by dissolving a chemical precursor solution in water or in mixed water and organic solvent and then reacting chemical precursor solution 1 with one or more compounds chosen from a group comprising ethyleneamine with a concentration of a resulting solution being at least 1% by weight of the surfactant solution, wherein: said chemical precursor solution 1 is formed by a reaction of a complex alkyl compound with an acid chosen from a group comprising polyphosphoric acid (PPA), phosphoric acid, sulfuric acid, and sulfonic acid, and a ratio by weight of the complex alkyl compound to the acid is at least 0.01 but less than 20; wherein the complex alkyl compound is chosen from a group comprising ethoxylated fatty alcohols, fatty alcohols, alcohols, ethoxylated alcohols, ethoxylated phenol, ethoxylated alkylphenol, alkyl polyglycoside, and alkyl aryl.
  2. The surfactant solution according to claim 1, wherein the ethyleneamine is chosen from a group comprising ethylenediamine (EDA), diethylenetriamine (DETA), piperazine (PIP), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), and pentaethylenehexamine (PEHA); and the chemical precursor solution is chosen from a group comprising fatty alcohol phosphate solution, ethoxylated fatty alcohol phosphate solution, fatty alcohol polyphosphate solution, ethoxylated fatty alcohol polyphosphate solution, fatty alcohol sulfonate solution, fatty alcohol sulfate solution, and ethoxylated fatty alcohol sulfate solution, wherein the ethoxylated fatty alcohol or fatty alcohol has 8 to 18 carbon atoms.
  3. A fluorine free foam (FFF) composition comprising water and the surfactant solution according to claim 1 or 2, wherein a pH of the fluorine free foam solution is at least 5.5 and less than 8.5.
  4. The fluorine free foam composition according to claim 3, additionally containing 0.1% to 4% by weight of a thickener chosen from a group comprising fumed silica, xanthan gum, diutan, scleroglucan, heteropolysaccharide, locust bean gum, partially-hydrolyzed starch, and guar gum; and additionally containing 0.1% to 4% by weight of an organic solvent.
  5. The fluorine free foam composition according to claim 4, wherein the organic solvent is glycol ether selected from a group comprising ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol phenyl ether, diethylene glycol methyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether; and/or the organic solvent comprises any of propylene oxide based materials.
  6. The fluorine free foam composition according to claim 5, wherein the propylene oxide based material is selected from one or more of propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol t-butyl ether, propylene glycol phenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol dimethyl ether, tripropylene glycol methyl ether, tripropylene glycol n-butyl ether, propylene glycol methyl ether acetate, and dipropylene glycol methyl ether acetate.
  7. The fluorine free foam composition according to any one of claims 3-6, wherein said surfactant solution is made by reacting said chemical precursor solution with ethyleneamine, and wherein said fluorine free foam composition has the properties of foaming agent and flame retardance.
  8. A mixture of a surfactant with ethyleneamine polyphosphate (EAPPA), wherein the surfactant is the surfactant solution according to claim 1 or 2, or the fluorine free foam composition according to any one of claims 3-6, and the amount of the ethyleneamine polyphosphate is from 1% to 99% by weight of the mixture.
  9. An aqueous fire extinguishing fluorine free foam (FFF) in the form of a mist, comprising the fluorine free foam composition of any one of claims 3-7, the aqueous fire extinguishing fluorine free foam having a expansion ratio greater than 2 but less than 20 and a water content being at least 45% but less than 99%, wherein the mist consists of droplets with a volume median diameter less than 1500 micron, or less than 600 micron, or less than 400 micron, or less than 200 micron, or less than 75 microns.
  10. The aqueous fire extinguishing fluorine free foam according to claim 9, wherein the mist is delivered by a system comprising a Venturi type foam former with at least one boom with at least two nozzles where the boom is projected into flames and operating variables of the system and composition of the aqueous fire extinguishing fluorine free foam are such to discharge the mist of the aqueous fire extinguishing fluorine free foam with expansion ratio of at least 3.
  11. The aqueous fire extinguishing fluorine free foam according to claim 10, wherein the expansion ratio is at least 5 and the foam is made with either water or sea water.
  12. The aqueous fire extinguishing fluorine free foam according to any one of claims 9-11, wherein the aqueous fire extinguishing fluorine free foam in the form of a mist has the properties of cooling the flames and reacting with the flame plasma radicals and ions.

Description

Field of Invention: Fluorine free foam has been made by forming a surfactant with flame retardant properties. This surfactant mixed with water forms foam with expansion ratios higher than 5. The foams are effective in extinguishing gasoline tank fires especially if applied as a mist with a large footprint. This foam reacts with the gasoline flames as intumescent char is observed on the surface of the tank after the fire is put out. Background of Invention: Aqueous film forming foams (AFFF) are water-based and frequently contain hydrocarbon-based surfactant such as sodium alkyl sulfates and fluorosurfactants, such as fluorotelomers, perfluorooctanoic acid (PFOA), or perfluorooctanesulfonic acid (PFOS). Perfluorooctanoic acid -also known as C8 or C6-is a perfluorinated carboxylic acid produced and used worldwide as an industrial surfactant in chemical processes. These fire fighting foams have been the preferred method for application to flammable liquid fires. Fluorine free foams often using surfactants such as sodium alkyl sulfate are less effective. However, it became clear that per fluorinated compounds such as PFOS and PFOA are extremely persistent in the environment, and toxicological studies have linked the chemicals to serious negative effects on human health. Their use in the EU has been restricted since 2006 and the Stockholm Convention listed PFOS and its related substances as persistent organic pollutants that are to be phased out. A further restriction on the manufacture, use and marketing of PFOA and its related substances, under REACH, was also adopted in 2017 by the European Commission. There is a growing body of scientific evidence that PFCs may be toxic to humans and to ecosystems. Some PFCs (PFOS and PFOA) are being phased out because of concerns about their safety. Many companies list only "proprietary fluorosurfactants mixtures" as ingredients in fire fighting foams A per fluorinated compound (PFC) per- or polyfluoroalkyl chemical is an organofluorine compound containing carbon-fluorine bonds and C-C bonds but also other heteroatoms. PFCs, also known as perfluorinated chemicals, have properties that represent a blend of fluorocarbons (containing only C-F and C-C bonds) and the parent functionalized organic species. For example, perfluorooctanoic acid functions as a carboxylic acid but with strongly altered surfactant and hydrophobic characteristics. Fluorosurfactants are ubiquitously used in Teflon, water resistant textiles and fire-fighting foam. The presence of perfluorinated compounds (PFCs) in source waters and drinking water is of growing concern to water professionals. This group of organic compounds, used for industrial and consumer applications such as nonstick coatings and firefighting foams, has potential health implications for humans and wildlife. PFCs are extremely persistent. Researchers are finding serious health concerns about PFCs, including increased risk of cancer. PFOA is a likely human carcinogen; it causes liver, pancreatic, testicular, and mammary gland tumors in laboratory animals. PFOS's half-life is estimated at more than 8 years. An alternative halogen free environmentally friendly fire fighting technology for application to flammable liquid fires is of need. A surfactant composition or surfactant solution with the properties of foaming agent and flame retardance has been made by making a new chemical precursor which is reacted with an ethyleneamine. This surfactant mixed with water, a thickening agent and organic solvent results in a fluorine free foam (FFF) that intumeses when subjected to a flame. This fluorine free foam (FFF) in the form of a mist or single stream can extinguish flammable liquid fires and class A fires. It will be shown that foam in the form of a mist can be applied with a boom to have a large footprint and more easily extinguish a flammable liquid fire than standard technology of a single stream. Summary: To form a FFF, the first step is to form a chemical precursor solution, comprising a chemical precursor solution 1 and a chemical precursor solution 2, wherein the chemical precursor solution 1 is formed by a reaction of a complex alkyl compound with an acid chosen from a group comprising polyphosphoric acid (PPA), phosphoric acid, sulfuric acid, and sulfonic acid, and a ratio by weight of the complex alkyl compound to the acid is at least 0.01 but less than 20; the chemical precursor solution 2 is formed by a reaction of complex alkyl sulfate ester or complex alkyl phosphate ester with the polyphosphoric acid, and a ratio by weight of the complex alkyl sulfate ester or the complex alkyl phosphate ester to the polyphosphoric acid is at least 0.01 but less than 20; and the complex alkyl compound is chosen from a group comprising ethoxylated fatty alcohols, fatty alcohols, alcohols, ethoxylated alcohols, ethoxylated phenol, ethoxylated alkylphenol, alkyl polyglycoside, and alkyl aryl. It is preferred that the reaction to form the chemical pre