Fluorine-free surfactants and foam compositions

Abstract

An alternative to fluorine-containing aqueous film-forming foam (AFFF) is needed. An ethylene amine salt of a chemical precursor solution is prepared that is a surfactant with foaming and fire-retarding properties. The chemical precursor solution is formed by reacting a complex alkyl compound with sulfuric acid or polyphosphoric acid. Foams made using this surfactant have a large coverage area to overcome poor diffusion coefficients and can successfully extinguish fuel fires.

Description

TECHNICAL FIELD

[0001] Fluorine-free foams are made by forming a surfactant that has flame retardant properties. This surfactant, when mixed with water, forms a foam with an expansion ratio greater than 5. This foam is very effective in extinguishing gasoline tank fires, especially when applied as a mist with a large footprint. The foam reacts with the gasoline fire and, after the fire is extinguished, expanded char can be observed on the tank surface. BACKGROUND

[0002] Aqueous film forming foams (AFFF) are water-based and typically contain hydrocarbon-based surfactants, such as sodium alkyl sulfate, and fluorine-containing surfactants, such as fluorotelomer, perfluorooctanoic acid (PFOA), or perfluorooctanesulfonic acid (PFOS). Perfluorooctanoic acid (also known as C8 or C6) is a perfluorinated carboxylic acid that has been produced and used globally as an industrial surfactant in chemical processes. These fire-fighting foams are the preferred method of application to flammable liquid fires. Fluorine-free foams, which typically use surfactants such as sodium alkyl sulfate, are less effective.

[0003] However, it is clear that perfluorinated compounds such as PFOS and PFOA have a very strong persistence in the environment, and toxicological studies have shown that these chemicals have serious negative effects on human health. Since 2006, the European Union has restricted their use, and the Stockholm Convention has listed PFOS and related substances as persistent organic pollutants that should be phased out. The European Commission passed further restrictions on the production, use, and sale of PFOA and related substances under REACH in 2017.

[0004] There is increasing scientific evidence that PFCs can be toxic to humans and ecosystems. Due to concerns about their safety, some PFCs (PFOS and PFOA) are being phased out. Many companies only list "proprietary fluorosurfactant mixtures" as ingredients of fire-fighting foams.

[0005] Perfluorinated compounds (PFCs) (perfluoro or polyfluoroalkyl chemicals) are organic fluorine compounds that contain C-F bonds and C-C bonds, as well as other heteroatoms. PFCs, also known as perfluorochemicals, have properties that exhibit a mixture of carbon fluorides (containing only C-F bonds and C-C bonds) and the parent functional organic. For example, perfluorooctanoic acid acts like a carboxylic acid, but the surfactant and hydrophobic properties are strongly changed. Fluorine-containing surfactants are widely used in Teflon, water repellent textiles, and fire-fighting foams.

[0006] Perfluorinated compounds (PFCs) found in source water and drinking water are of increasing concern to water professionals. These organic compounds, used in industrial and consumer products such as non-stick coatings and fire-fighting foams, have potential impacts on human and wildlife health. PFCs are extremely persistent. Researchers have found that PFCs pose serious health risks, including increased risk of cancer. PFOA is likely a human carcinogen; it causes liver, pancreas, testicular, and mammary gland tumors in experimental animals. The half-life of PFOS is estimated to be more than 8 years.

[0007] There is a need for an alternative, environmentally friendly, halogen-free fire extinguishing technology for flammable liquid fires. A surfactant composition or surfactant solution with foaming and fire-retardant properties is prepared by reacting a new chemical precursor with an ethylene amine. The surfactant is mixed with water, a thickening agent, and an organic solvent to form a fluorine free foam (FFF) that expands upon exposure to a flame. This thin mist or single stream fluorine free foam (FFF) can extinguish flammable liquid fires and Class A fires. It is shown that the thin mist foam can be sprayed using a boom, covers a larger area, and is easier to extinguish flammable liquid fires compared to standard technology of single stream foam. SUMMARY

[0008] To form the FFF, the first step is to form a chemical precursor solution, including chemical precursor solution 1 and chemical precursor solution 2, wherein chemical precursor solution 1 is formed from a complex alkyl compound reacted with an acid selected from the group including polyphosphoric acid (PPA), phosphoric acid, sulfuric acid, and sulfonic acid, the complex alkyl compound to acid weight ratio is at least 0.01 but less than 20; chemical precursor solution 2 is formed from a complex alkyl sulfate or a complex alkyl phosphate reacted with polyphosphoric acid, the complex alkyl sulfate or complex alkyl phosphate to polyphosphoric acid weight ratio is at least 0.01 but less than 20; the complex alkyl compound is selected from the group including ethoxylated fatty alcohols, fatty alcohols, alcohols, ethoxylated alcohols, ethoxylated phenols, ethoxylated alkyl phenols, alkyl polyglycosides, and alkyl aryls. Preferably, the reaction to form the chemical precursor solution is conducted at a temperature between room temperature and 400°F, the grade of polyphosphoric acid is 105% to 118%, the concentration of phosphoric acid and sulfuric acid is at least 80% each, and the pH of a 10 wt% aqueous solution of the chemical precursor is less than 2.2.

[0009] The surfactant composition is formed from one or more compounds selected from the group including ethylene amines, alkali metals, ammonia, and alkanol amines reacted with 1) one or more of chemical precursor solutions 1 and 2, and 2) one or more compounds selected from the group including complex alkyl phosphates, complex alkyl sulfates, and complex alkyl sulfonates, the pH of a 10 wt% surfactant composition in water or in water and an organic solvent is at least 3.5 and less than 8.5.

[0010] The surfactant solution is formed by 1) dissolving the surfactant composition in water or in a mixture of water and an organic solvent, or 2) dissolving the chemical precursor solution in water or in a mixture of water and an organic solvent, then reacting chemical precursor solution 1 or chemical precursor solution 2 with one or more compounds selected from the group including ethylene amines, alkali metals, ammonia, and alkanol amines, the resulting solution has a concentration of at least 1 wt% of the surfactant solution. If the chemical precursor is prepared from phosphoric acid, polyphosphoric acid, or sulfuric acid and reacted with ethylene amines, both the surfactant solution and the surfactant composition have flame retardant properties. Polyphosphoric acid is preferred because it has greater self- swelling properties.

[0011] The fluorine-free foam (FFF) composition is formed from water and the surfactant solution. Thickening agents, other surfactants, and organic solvents can be added. DETAILED DESCRIPTION

[0012] The foam composition is primarily composed of water, organic solvent, surfactant, and thickener. Additionally, the organic solvent can refer to one or more organic solvents, the surfactant can refer to one or more surfactants, and the thickener can refer to one or more thickeners. The terms complex alkyl and complex alkyl compound are used interchangeably. The terms complex alkyl phosphate and complex alkyl phosphate solution are used interchangeably. The terms complex alkyl polyphosphate and complex alkyl polyphosphate solution are used interchangeably. The terms complex alkyl sulfate and complex alkyl sulfonate are used interchangeably. The terms dodecyl and lauryl are used interchangeably. A solution is a homogeneous mixture of two or more substances. A solution can exist in any phase. A solution is composed of a solute and a solvent. The solute is the substance that is dissolved in the solvent. A flame retardant is a chemical applied to a material to prevent the occurrence of a fire or to retard the spread of a fire. A blowing agent is a substance that promotes the formation of foam, such as a surfactant. A wetting agent is a chemical that can be added to a liquid to lower its surface tension and make it spread and penetrate more effectively on a surface. In chemistry, a precursor is a chemical compound that participates in a chemical reaction to produce another compound. The pH of a composition will typically be measured. Unless otherwise specifically stated, the measurement will be 10% by weight of the composition in water. Components are typically discussed and disclosed in %. Unless specifically stated, all are by weight percent of the ingredient, not by volume percent. Soluble means that the ingredient will dissolve and blend with the substance it is put into. In short, it will become a uniform whole. Dispersible means that the ingredient will not blend with the substance it is put into, but if treated in a specific way, it can be dispersed (spread evenly). A cloudy solution is formed, but no separation occurs.

[0013] The terms complex alkyl phosphate solution and complex alkyl polyphosphate solution are not used interchangeably. The composition formed by mixing together a complex alkyl phosphate solution and a PPA and then reacting with an ethylene amine is not used interchangeably with the composition formed by mixing or melting together an ethylene amine, a complex alkyl phosphate solution, and an EAPPA. The term "ester" has a specific meaning in chemistry. The term complex alkyl phosphate (CAPE) has a structure consistent with that definition, i.e., having mono- and di-ester linkages. The term complex alkyl polyphosphate solution here refers to a compound formed by reacting a complex alkyl compound and a polyphosphoric acid in a wide range of ratios. The exact nature of the chemical bonding is not known. The term complex alkyl phosphate solution here refers to a compound formed by reacting a complex alkyl compound and phosphoric acid in a wide range of ratios. The exact nature of the chemical bonding is not known.

[0014] Ethyleneamine polyphosphate (EAPPA) is formed by the direct reaction of ethyleneamine (EA) and polyphosphoric acid (PPA) at near theoretical acid to base ratios, with the reaction taking place without water or other solvents. This form of EAPPA can be made by reacting any grade of PPA, including PPA that has undergone condensation. The synthesis without dopants is detailed in US 10501602. The synthesis using dopants such as fumed silica is disclosed in PCT / 19 / 034077. Neither of these references discloses that this aqueous composition containing hydrophilic fumed silica promotes adhesion and inhibits dripping from surfaces, which is most helpful for applying these solutions for fire suppression. US 7, 138,443, US 8212073, WO 2011 / 049615 (PCT / US12 / 000247), PCT / US2003 / 017268, and US 8703853 disclose methods of synthesizing flame retardants using polyphosphoric acid. US 7569155 discloses a fluorine-free foam, which is prior art. PCT / US20 / 52061 discloses the use of EAPPA solutions to form thin mists and foams. Provisional applications and application dates are 63331795 (April 16, 2022), 63305650 (February 1, 2022), 63277466 (November 9, 2021), 63226717 (July 28, 2021). The entire disclosures are incorporated herein by reference. The FS can be added to the PPA prior to the synthesis of the EAPPA. The FS can be added directly to the aqueous solution after synthesis. Preferably, the EAPPA is made first and then diluted with water to the desired concentration. It is also possible, but not preferred, to dilute the polyphosphoric acid with water and then add the ethyleneamine to make the desired product. The most preferred EAPPA is made from PPA and the following ethyleneamines: ethylenediamine (EDA), diethylenetriamine (DETA), piperazine (PIP), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), and pentaethylenehexamine (PEHA).

[0015] No references have been found that attempt to form compounds with both flame retardant and surfactant properties. No references have been found that use compounds with both surfactant and flame retardant properties to form fluorine-free fire extinguishing foam. Alkali metal salts are known not to have flame retardant properties. Amine salts of phosphates are well known flame retardant polymers. To our knowledge, amine salts of sulfates have not been found to be useful as flame retardant polymers.

[0016] Ethyleneamines are defined herein as ethylenediamine and polymeric forms of ethylenediamine, including piperazine and its analogs. A comprehensive review of ethyleneamines can be found in the Encyclopedia of Chemical Technology, Volume 8, pages 74-108. Ethyleneamines encompass a broad range of multifunctional, multi-reactive compounds. The molecular structure can be linear, branched, cyclic, or a combination of these. Examples of commercially available ethyleneamines are ethylenediamine (EDA), diethylenetriamine (DETA), piperazine (PIP), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), and pentaethylenehexamine (PEHA). Other ethyleneamine compounds that can be applied as part of the general term ethyleneamines (EA) are aminoethylenepiperazin (EAP), 1,2-propanediamine, 1,3-diaminopropane, iminobispropylamine, N-(2-aminoethyl)-1,3-propanediamine, N,N'-bis-(3-aminopropyl)-ethylenediamine, dimethylaminopropylamine, and triethylenediamine. Ethyleneamine polyphosphates can be formed from any of these ethyleneamines.

[0017] Alkanolamines are compounds that contain hydroxyl (-OH) and amino (-NH2, -NHR, and -NR2) functional groups on an alkane backbone, such as triethanolamine (TEA) and 2-amino-2-methyl-1-propanol (AMP).

[0018] Polyphosphoric acid (PPA) is an oligomer of H3PO4. High purity PPA is prepared by dehydration of H3PO4 at high temperatures or by heating P2O5 dispersed in H3PO4. The equilibrium of these reactions produces chains of varying length and distribution. The dehydration method tends to produce short chains, while the dispersion method generally produces chains of more than 10 repeat units, which is more preferred in the preparation of the compositions of the present invention. In the preparation of PPA, the reaction of P2O5 and 85% concentration phosphoric acid has used many different temperatures.

[0019] PPA comes in various grades, which are confusing in their nomenclature since the percentages can exceed 100%. 100% phosphoric acid contains 72.4% P2O5, calculated on the basis of the chemical formula weight ratio P2O5 / H3PO4. Likewise, pyrophosphoric acid (H4P2O7) contains 79.8% P2O5, calculated on the basis of the ratio P2O5 / H4P2O7. The ratio of these P2O5 contents provides a relative phosphoric acid content, which for pyrophosphoric acid is 79.8% / 72.4% = 110%. PPA is difficult to pour and stir at room temperature due to high viscosity, but is easier to handle at temperatures above 60°C.

[0020] Production of PPA provides a chain length distribution, where the number of repeat units n in a PPA chain varies from chain to chain. The 105% PA grade from Innophos Corporation contains mostly short monomer and dimer segments, ortho (54%), pyro (41%), and 5% triphosphoric acid, and is easy to pour, and is not expected to provide a route to high molecular weight EAPPA. In the higher 115% grade, there is almost no monomer left, since most of the chain length is 2-14 units. This increase in chain length leads to chain entanglement, which is the reason for the increased viscosity of the higher grades. The 117% grade contains (3% ortho, 9% pyro, 10% triphosphoric acid, 11% tetraphosphoric acid, 67% higher acids); the 115% grade contains (5% ortho, 16% pyro, 17% triphosphoric acid, 16% tetraphosphoric acid, 46% higher). These products are from Innophos Corporation of Trenton, NJ. All grades of PPA, regardless of how they are formed, are claimed.

[0021] Commercial polyphosphoric acid contains some ortho and pyro phosphoric acid. By heating and simultaneously vacuuming the polyphosphoric acid, the amount of ortho and low molecular weight PPA can be significantly reduced, resulting in a higher molecular weight, more viscous polyphosphoric acid. Concentrated polyphosphoric acid and commercial polyphosphoric acid are both polyphosphoric acids.

[0022] EAPPA is prepared directly by the reaction of ethylene amine with polyphosphoric acid, the ratio of PPA to ethylene amine being chosen so that the pH of a 10% by weight aqueous solution of the resulting composition is at least 2.7. Preferably, the pH is at least 3.5. More preferably, the pH is 4.2. Most preferably, the pH is greater than or equal to 5.0.

[0023] Alkyl polyglycosoide is a biodegradable ingredient derived from plant starch and fatty alcohols in coconuts. Alkyl phosphate esters belong to a class of organic compounds called organophosphates. They are esters of phosphoric acid, H3PO4, and the corresponding alcohol. Ethoxylated alkyl phosphate esters are formed from ethoxylated alcohols.

[0024] A gel is a semi-solid that can have properties ranging from soft and loose to hard and tough. Gels are defined as a substantially dilute cross-linked system that will not flow at a steady rate under the influence of an applied stress.

[0025] Intumescence of a coating, as used in the context of this specification, means to swell upon heating or exposure to a flame, thereby protecting the material underneath during a fire event. Fireproof coatings typically contain adhesives such as ammonium polyphosphate, pentaerythritol, di-pentaerythritol, melamine, and vinyl acetate copolymer. When exposed to heat or flame, the coating turns into a lightweight char or a cellular carbonaceous foam due to chemical reactions of the three main ingredients. It is the unique aspect of the ethylene amine polyphosphates that these compounds intumesce from heat or flame without the need for melamine or pentaerythritol. This property is called self- intumescence.

[0026] A mist is suitable for fine particles of water suspended in air, floating or falling slowly in the form of tiny droplets. A vapor is composed of single gas-phase molecules, while a mist droplet is in the liquid phase, containing thousands or millions of molecules. Common examples of mists are spray boxes, clouds, and fogs, where the mist droplets are very small. Their average diameter is usually only 10-15 microns (1 micron = 1 / 1000 mm), but in any one cloud, the size of individual droplets ranges widely, from 1 micron to 100 microns in diameter. Haze, mist, fog, and smog refer to an atmospheric condition that makes the air near the earth lose its transparency. A vapor is water vapor that forms when water is heated, creating a white mist in the air composed of tiny droplets.

[0027] Mist is defined here as a cloud of tiny droplets of fire extinguishing solution. Mist is not a very precise term, but it is formed of tiny droplets, and the reduction in visibility depends on the size and density of the droplets. Droplet size is measured in microns. One micron is 1 / 1000 mm (micron), about 1 / 25000 of an inch. To put this in perspective, a strand of hair is about 100 microns in diameter. Spray droplets smaller than 150 microns tend to drift. High pressure, such as 4000 PSI, can overcome the problem of slight drift.

[0028] In PCT / US20 / 52061 it is stated that “EAPPA solutions need to form a mist to be effective for direct use on any type of fire. The size of the droplets in the mist is also critical. The Volume Median Diameter (VMD) refers to the midpoint value (median) of the droplet size, i.e. half of the spray volume is of droplets smaller than the median, and the other half is of droplets larger than the median. If the droplets are larger, the effectiveness of the spray is greatly reduced. As the droplet size decreases, the fire extinguishing efficiency increases rapidly”. It will be shown here that a mist-like foam is effective and uses the same equipment.

[0029] In agriculture, there are devices that can spray water solutions as a mist. The mist droplet size is defined by VMD. Very fine is XF and the droplet size is less than 60 microns. Very fine is VF and the droplet size is 60-145 microns. Fine is F and the droplet size is 145-225 microns. Medium is M and the droplet size is 226-325 microns. Coarse is C and the droplet size is 326-400 microns. Very coarse is VC and the droplet size is 401-500 microns. Extra coarse is EC and the droplet size is 501-650 microns. Ultra coarse is UC and the droplet size is greater than 650 microns.

[0030] To achieve our purpose, we require a droplet size of 1500 microns or less, or preferably less than 600 microns, or more preferably less than 400 microns, or even more preferably less than 200 microns, or most preferably less than 75 microns, to form a mist of fire extinguishing liquid or fire extinguishing foam when sprayed under pressure through a nozzle with tiny holes. The nozzle can have a variety of shapes and droplet sizes for the mist. We exclude the use of a continuous stream of liquid from a large hose or liquid dripping from an airplane. In agriculture, the selection of the proper nozzle is carefully considered for drift, plant coverage, penetration of plant foliage, and delivery equipment to achieve the best droplet size of the chemical applied to the soil and plants.

[0031] The EAPPA water solution is made with ethylene amine and is called PNS. All examples of PNS are made using 115% grade PPA reacted with DETA. It is also possible to dilute the PPA with water and then add EA to form the EAPPA water solution, although this method is not preferred. The water will break down the molecular weight, especially as the temperature increases, so that the solution is of lower molecular weight polymer without free water. The solutions reported in the examples are made by diluting PNS made from 115% PPA and DETA. Such examples can be made directly by using PPA of comparable grade to the PPA. We use this high molecular weight method because the solids tend to minimize cost, storage, and shipping problems. If desired, the solids can be converted to PNS solution. Compounds made by mixing PPA and one or more complex alkyl compounds together and then reacting with EA have both fire retardant properties and surfactant properties and are called PNS-F.

[0032] A free radical is a chemical species that contains an unpaired electron. Generally, free radicals are highly reactive and can very rapidly reform new bonds. Free radicals can be electrically neutral, positively charged (radical cations), or negatively charged (radical anions). Ions carry an electric charge, which means that the number of electrons and protons do not match. Electrons carry a negative charge and protons carry a positive charge. Ions seek opposite charges to become neutral.

[0033] At a certain point in the combustion reaction, known as the ignition point, a flame is produced. The flame is the visible part of fire. If hot enough, a gas can be ionized to produce a plasma. A flame (from flamma in Latin) is the visible gaseous part of a fire. It is caused by a highly exothermic reaction, which occurs in a thin zone. Very hot flames are hot enough to have an ionized gaseous component with sufficient density to be considered a plasma. The high temperature of the flame causes the vaporized fuel molecules to break down, forming various incomplete combustion products and free radicals, which then react with each other. Enough energy in the flame excites the electrons in some transient reaction intermediates (such as the methylidyne radical (CH) and the diatomic carbon (C2)), which results in the emission of visible light when these species release their excess energy. As the combustion temperature of the flame increases (if the flame contains small particles of unburned carbon or other materials), the average energy of the electromagnetic radiation emitted by the flame also increases. The chemical kinetics occurring in a flame are very complex, often involving a large number of chemical reactions and intermediates, most of which are free radicals. A fire is an example of a chain reaction. A burning candle or other fire is also an example of a chain reaction.

[0034] The fire point of a fuel refers to the lowest temperature at which the vapors of the fuel will continue to burn for at least 5 seconds after being ignited by a standard-sized open flame. At the flash point, a lower temperature, a substance will briefly ignite, but the speed at which the vapors are produced can not sustain the fire. The flash point is an important concept in fire investigation and firefighting, as it is the minimum temperature at which a liquid is considered to be at risk of fire. Gasoline has a flash point of about -45°F, diesel fuel has a flash point of 126-205°F, and heptane has a flash point of 25°F. Therefore, a gasoline fire is much more dangerous than a diesel fire.

[0035] Vapor pressure is the pressure caused by the evaporation of a liquid. The three common factors that affect vapor pressure are surface area, intermolecular forces, and temperature. The vapor pressure of a molecule is different at different temperatures. The most common way to measure the vapor pressure of gasoline is the Reid vapor pressure (RVP). This refers to the pressure, in psi (pounds per square inch) or kPa (kilopascals), required to keep a liquid from vaporizing when the temperature is 100°F (37.8°C). Gasoline has an RVP of 7.8 to 16 PSI, forming a large amount of vapor. Diesel fuel has a much lower RVP of 0.03 to 0.1 PSI, with very little vapor. Heptane has an RVP of about 1 PSI, almost the same as water, with a moderate amount of vapor. Jet fuel has an RVP of about 0.21 PSI, with very little vapor. Therefore, gasoline is very easy to ignite, even at very low temperatures, and is much more flammable than diesel or jet fuel. From the flash point and the Reid vapor pressure, it is very important for the EAPPA technology to be able to extinguish a gasoline fire.

[0036] Nozzles break up liquid into droplets, form a spray pattern, and propel the droplets in the appropriate direction. The most common nozzles are flat fan, flood, air induction, hollow cone, full cone, and others. Flat fan nozzles are widely used for fan-shaped broadcast spraying of herbicides and are used in this specification. There are multiple subtypes, such as standard flat fan, uniform flat fan, low pressure flat fan, extended range flat fan, dual orifice, and others, as used herein. Surprisingly, the foam emitted through these nozzles forms a mist consisting of tiny foam droplets, and this mist has a high expansion rate.

[0037] There are dozens of nozzles, and hundreds of sizes and materials of construction. The simplest single-fluid nozzle is a flat orifice. This nozzle usually produces little atomization, just a directed stream of liquid. If the pressure drop is high, at least 25 bar (2500 kPa, 363 PSI), the material is usually finely atomized, as in diesel injectors. At lower pressures, this nozzle is often used as a fixed-position composite nozzle or as a rotary nozzle for tank cleaning. Higher P values will reduce droplet size. Smaller nozzles also produce smaller droplets. Our FR foam technology works best as a fine droplet size type mist. When spraying water, the pressure is increased four-fold, resulting in a doubling of the flow rate. The most common nozzles are flat fan, hollow cone, full cone, and streamline.

[0038] For flat fan nozzles, the shaped orifice has a hemispherical inlet and a V-shaped notch outlet, which disperses the liquid stream along the V-shaped notch axis. This nozzle is called a flat tip nozzle, with a fan-shaped spray. The flat fan spray pattern is suitable for many spray applications, such as paint spraying and agricultural spraying. Very small droplets are actually decelerated as they exit the nozzle. Small droplets dry out quickly, losing the contribution of water. As the density of the sprayed liquid increases, the spray angle decreases, which is important for spraying fire-fighting solutions.

[0039] Most companies identify their flat fan nozzles with four or five digits. The first digit is the spray angle, and the other digits indicate the discharge of water in gallons per minute (GPM) at a nominal pressure. For example, an 8005 has an 80-degree spray angle and will apply 0.5 GPM at a nominal pressure of 40 psi. This specification uses an 8003, which has an 80-degree spray angle and 0.3 GPM of water at 40 psi. However, the spray rate is different at different pressures and different liquids. An 8003 flat fan is hooked up to a hose on a fire extinguisher cart with 100 PSI of water in the cart. At 100 PSI, the 8003 has a spray rate of 0.51 GPM, and the 8006 has a spray rate of 0.97 GPM, significantly higher than the manufacturer’s data at 40 PSI. For a pressure washer that operates at 4000 PSI, the spray rate for an 8003 and 8006 is 2.3 GPM. If a Y-connector is used to have both nozzles, the spray rate is the same. Unexpectedly, the spray rate for a flat fan on a 4000 PSI pressure washer is the same.

[0040] It turns out that hollow cone nozzles are preferred over flat fan nozzles. Hollow cone nozzles provide smaller droplet sizes and less impact on the surface to which the fuel is applied. A full discussion will follow later in this specification.

[0041] Just as there are many types of nozzles, there are many types of sprayers. One of the most common forms of applying pesticides is with mechanical sprayers, especially in traditional agriculture. Droplet size can be varied by using different nozzle sizes, or by varying the pressure at which the droplets are applied, or both. Large droplets are less affected by drift, but more water is needed per unit of area covered. Small droplets can maximize contact with the target organism due to electrostatic effects, but require very still wind conditions. Fog is a subcategory of mist.

[0042] Even small changes in droplet diameter make a huge difference in droplet weight. Droplet weight doubles when the diameter increases from 150 microns to about 190 microns. Droplet weight increases 4-fold when the diameter increases from 150 microns to about 240 microns. Doubling the diameter to 300 microns increases the weight and volume 8-fold. Heavier droplets fall faster and are less affected by air flow.

[0043] Gasoline is not soluble in water. Gasoline is a complex mixture of nonpolar compounds such as long-chain hydrocarbons. Water is a polar molecule. The general solubility rule is “like dissolves like,” i.e., polar dissolves polar, nonpolar dissolves nonpolar.

[0044] Power washing is the use of a high-pressure water jet to remove loose paint, mold, grime, dust, mud, chewing gum, and dirt from surfaces and objects (e.g., buildings, vehicles, and concrete surfaces). A power washer uses a very hot high-pressure jet of water to blast away dirt and material from outdoor surfaces. The capacity of a mechanical power washer is measured in gallons or liters per minute, usually designed into the pump. The pressure is measured in pounds per square inch, pascals or bars, designed into the pump, but can be varied by adjusting the unloader valve. Machines producing 750 to 30,000 psi (5 to 200 MPa) or more are available. Typically, a power washer sucks in ordinary water from a garden hose, the pump accelerates the water to high pressure, and then the water is ejected at high speed from the hose through a nozzle smaller than the hose diameter. The water pressure is typically 1550-3000 PSI. Power washers are primarily used for cleaning, not agricultural spraying or firefighting.

[0045] It has been discovered that a preferred method of making very fine foam mist is to use a modified power washer (1500 PSI to 4000 PSI) and a misting nozzle. Instead of a garden hose, a 100 PSI fire extinguisher tank or a 20 gallon tank with a bladder containing pressurized solution at 50-100 PSI is connected to the power washer as a source. One or more spray heads from agricultural spraying are used instead of the conventional spray head to produce a fan mist of 80° to 100°. In the agricultural field, these spray heads are rated by the amount of water (GPM) that is sprayed at 40 PSI. Using such a spray head with an 80° spray angle, the spray rate is 0.1 (8001) to 0.3 (8003) to 2.0 (8020) gallons per minute at 40 PSI. Commercial systems are available where a large tank is mounted on the power washer and multiple hoses are operated simultaneously. While the VMD of the power washer configuration has not been measured, it is expected that the VMD of the water is very small. PNS is a polymer and has a much higher surface tension. It takes more pressure to produce a foam mist containing PNS than water.

[0046] Monoesters are R-O-P=O-(OH)2. Diesters are (R)2-O-P=O-(OH). For alcohol-based phosphates, R is from an alcohol. For ethoxylated alcohol-based phosphates, R is from an ethoxylated alcohol (alcohol-ethoxylate). For ethoxylated phenol-based phosphates, R is from a specific ethoxylated phenol. For ethoxylated alkyl phenol-based phosphates, R is from a specific ethoxylated alkyl phenol. Phenol (also called carbolic acid) is an aromatic organic compound with the molecular formula C6H5OH. Alkylphenols are a group of organic compounds obtained by the alkylation of phenol. The term usually refers to propylphenol, butylphenol, amylphenol, heptylphenol, octylphenol, nonylphenol, dodecylphenol, and related "long-chain alkylphenols" of significant commercial value.

[0047] Alcohol ethoxylates are formed by the reaction of a fatty alcohol and ethylene oxide:

[0048] ROH + nC2H4O → R(OC2H4) n OH, where n is preferably 1-18. Fatty alcohols (or long chain alcohols) are typically primary straight chain alcohols of high molecular weight, but can range from as few as 4-6 carbon atoms to as many as 22-26 carbon atoms, and are derived from natural fats and oils. The hydrophilic component of ethoxylated surfactants is currently based primarily on ethylene oxide (EO) or poly(ethylene oxide) (POE).

[0049] Polyethylene glycol (PEG) is a polyether compound extracted from petroleum and has a wide range of applications from industrial manufacturing to medicine. PEG is also known as polyethylene oxide (PEO) or polyoxyethylene (POE) depending on the molecular weight. The structure of PEG is generally represented as H-(0-CH2-CH2)n-OH.

[0050] Alkyl is a functional group of organic chemistry that contains only carbon and hydrogen atoms arranged in a chain. They have the general formula CnH2n+1. The definition of complex alkyl phosphates (CAPE) from U.S. Patent 6,696,399 is adopted here with some modifications. Complex alkyl refers to an organic compound selected from the group including fatty alcohols, ethoxylated fatty alcohols, ethoxylated phenols, alkyl polyglycosides, ethoxylated alkyl phenols, and alkyl aryls. The compound alkyl polyglycoside is added to the examples of complex alkyl. Accordingly, complex alkyl phosphates are selected from the group including mono- and di-alkyl phosphates, alcohol phosphates, ethoxylated alcohol phosphates, alkyl polyglycoside phosphates, ethoxylated alkyl phenol phosphates, ethoxylated phenol phosphates, alkyl polyglycoside esters, and alkyl aryl phosphates.

[0051] Accordingly, complex alkyl sulfates (CASE) are described as including alcohol sulfates, ethoxylated alcohol sulfates, ethoxylated alkyl phenol sulfates, and ethoxylated phenol sulfates. Complex alkyl sulfonates also have a similar definition accordingly. Complex alkyl includes compounds with and without ethoxylation.

[0052] In commerce, complex alkyl phosphate surfactants are produced by the reaction of fatty alcohols, ethoxylated fatty alcohols, ethoxylated phenols, or ethoxylated alkyl phenols with phosphating agents (orthophosphoric acid and phosphorus pentoxide). These commercial producers do not disclose the details of their production. The resulting surfactants are mixtures containing primarily mono- and di-alkyl phosphates, as described in the company data sheets. These compounds have a pH of at least 2, indicating the presence of a large amount of diester linkages. This definition assumes that one or two esters are formed for each phosphate. Alkyl aryl acid phosphates are produced by the reaction of phosphorus pentoxide and an alcohol. The same is true for the formation of alkyl aryl sulfonates.

[0053] We now describe several new chemical precursor solutions that are the core of the preferred compounds in this specification: 1) complex alkyl polyphosphate (CA-PPA) solutions, 2) complex alkyl phosphate (CA-PA) solutions, 3) complex alkyl phosphate polyphosphate (CAPE-PPA) solutions, 4) complex alkyl sulfate solutions (CA-SA) generated by reacting complex alkyl compounds with sulfuric acid (SA), 5) complex alkyl sulfonate solutions (CA-SFA) generated by reacting complex alkyl compounds with sulfonic acid (SFA). These solutions are anhydrous chemical precursors that can react with a variety of cations to form compounds with surfactant properties, wetting agents, emulsifiers, corrosion inhibitors, and antistatic properties with a wide range of applications. These solutions readily react with ethylene amines to provide fire retardant properties with a continuous range of surfactant and FR composition, where the ratio of fire retardant EAPPA to surfactant can be continuously varied over a wide range by varying the ratio of complex alkyl compounds to PA, PPA, SA, and SFA. Examples will show the behavior of these solutions for different complex alkyl compounds. Examples will be labeled CA-PA, CA-PPA, CA-SA, CA-SFA, CASE-PPA, or CAPE-PPA to easily distinguish the type of solution used. CAPE refers to examples where commercially available complex alkyl phosphate was used to make the foam composition and is different from CAPE-PPA. Sulfonic acid is not readily available and was not attempted.

[0054] The complex alkyl polyphosphate (CA-PPA) solution in this specification is defined as the compound formed by the reaction of polyphosphoric acid and a complex alkyl compound over a wide range of concentrations. The solution is made without phosphorus pentoxide or orthophosphoric acid. It is necessary to heat in a vessel to speed the reaction. The amount of heat required depends on the complex alkyl being reacted if needed. The compound formed by dissolving the polyphosphoric acid and the complex alkyl compound together in a heated vessel to form a clear solution with a slight tint will be called the complex alkyl polyphosphate (CA-PPA) solution. It is not presently known how many ester linkages are actually formed. The compound will show both flame retardant and foaming properties after reaction with EA. It is very difficult to determine the actual composition of the PPA because it is very complex. The complexity is due in part to the composition of the polyphosphoric acid which, as previously stated, inherently contains some orthophosphoric acid as well as pyrophosphoric, tripolyphosphoric and longer chains depending on the grade. We expect that there is significant steric hindrance in attempting to esterify the long chain PPA so that at least some of the phosphorus atoms will not have an ester linkage. The long chain PPA also has fewer bonds available to form esters. The orthophosphoric acid component inherent in the PPA should be available to form ester linkages. Commercial ethoxylated alcohol phosphates have a pH of about 2-2.5. Our complex alkyl polyphosphate solution has a lower pH (less than 1.95) indicating fewer ester linkages. The primary reaction that occurs with some complex alkyls can be the solvation of the PPA by the complex alkyl compound. Thus, our definition encompasses the composition formed by dissolving a complex alkyl compound in PPA, heating if necessary to form a clear solution, which is usually slightly brown in tint, with an unknown amount of formal ester linkages. It is likely that di- or tri-ester linkages are not present. The complex alkyl polyphosphate solution can be reacted with many different cations to be a new compound. Different cations are necessary for different applications. For soaps, the cation can be an alkali metal such as sodium or potassium. When both foaming and flame retardancy are necessary, an ethylene amine will be the cation. More generally, the cation is one or more compounds selected from the group including ethylene amine (EA), alkali metals, ammonia and alkanolamines.

[0055] The complex alkyl phosphate solution is formed from phosphoric acid (PA) reacted with a complex alkyl. These are precursors that can be reacted with various cations to form compounds with surfactant properties, wetting agents, emulsifiers, corrosion inhibitors and antistatic properties with a wide range of applications. This solution is different from the complex alkyl phosphate ester because it is formed without the use of phosphorus pentoxide at various ratios of acid to complex alkyl. The complex alkyl phosphate solution reacts with EA to produce a compound with surfactant and flame retardant properties. The ethylene amine complex alkyl phosphate ester formed by the reaction of ethylene amine with a commercial complex alkyl phosphate ester is different as shown below. The foaming properties are not as good as the complex alkyl phosphate (CA-PA) solution. The difference is attributed to the complex alkyl phosphate (CAPE) having about 50% di-ester linkages which reduces the ability to react with ethylene amine. The long chain PPA also has fewer bonds available to form esters. The orthophosphoric acid component inherent in the PPA should be available to form ester linkages. Commercial ethoxylated alcohol phosphates have a pH of about 2-2.5. Our complex alkyl polyphosphate solution has a lower pH (less than 1.95) indicating fewer ester linkages. The primary reaction that occurs with some complex alkyls can be the solvation of the PPA by the complex alkyl compound. Thus, our definition encompasses the composition formed by dissolving a complex alkyl compound in PPA, heating if necessary to form a clear solution, which is usually slightly brown in tint, with an unknown amount of formal ester linkages. It is likely that di- or tri-ester linkages are not present. The complex alkyl polyphosphate solution can be reacted with many different cations to be a new compound. Different cations are necessary for different applications. For soaps, the cation can be an alkali metal such as sodium or potassium. When both foaming and flame retardancy are necessary, an ethylene amine will be the cation. More generally, the cation is one or more compounds selected from the group including ethylene amine (EA), alkali metals, ammonia and alkanolamines.

[0056] A complex alkyl phosphate PPA (CAPE-PPA) solution is formed by dissolving PPA and a commercial complex alkyl phosphate together. This solution is different from a complex alkyl phosphate because it is formed at various ratios of acid to complex alkyl phosphate. This solution can react with any cation. Reaction with ethylene amine produces a compound that has both surfactant and flame retardant properties. The flame retardant properties of this compound are superior to ethylene amine complex alkyl phosphate.

[0057] A complex alkyl sulfate can be reacted with PPA to form a solution (CASE-PPA). This solution can then be reacted with EA to form more compositions with both foaming and flame retardant properties. For example, lauryl ether sulfate (LES) is dissolved with PPA or reacted with PPA to form a solution. By reacting the LES-PPA solution with EA a composition is formed that has both flame retardant and surfactant properties. Sulfates and sulfonates are more likely to have corrosion and environmental issues compared to phosphates, so this composition is not preferred.

[0058] Surfactant compositions or compounds are formed by reacting chemical precursors with EA to form compounds with FR and surfactant properties. Similar compounds without self- expansion properties can be made by reacting CA-SA, CA-PPA, CA-PA, and CAPE-PPA with ammonia, alkanolamines, and alkali metals as part of this invention. These compounds have less FR but can have excellent surfactant properties depending on the application.

[0059] These compounds with surfactant and flame retardant properties have been found to be useful in the following applications: 1) flame retardant polymers that require compounds with low sensitivity to moisture and melt into the polymer; 2) stopping wildfires where surfactant properties promote adhesion and spread on Class A fuels; 3) foams for fuel fires where foaming is necessary to stop rekindling or backdraft once the fuel fire is extinguished. Each application will require a different ratio of surfactant properties to flame retardant properties, and the preferred composition can also be different.

[0060] The gasoline used in all experiments was an octane of 87 gasoline, usually containing 10% ethanol, commonly referred to as E10. The MILSPEC gas was a pure gas without ethanol, also referred to as E0 gas. E10 gasoline burns hotter than MILSPEC gasoline and is more difficult to extinguish because of backdraft or rekindling issues.

[0061] PNS is prepared from 115% PPA according to claim 1 in US 10501602. PNS-F in this specification is prepared by reacting a CA-PPA solution with an ethylene amine. The only EA used in this specification is DETA, but other ethylene amines are suitable. PNS-F also includes any composition prepared by reacting an ethylene amine with any complex alkyl sulfate solution, any complex alkyl phosphate solution, and any complex alkyl sulfonate solution.

[0062] A working hypothesis was presented in PCT-US20-05206 that a thin mist of DETA PPA reacts with the flame in a fire to extinguish it by reacting with ions and radicals and suppressing the production of heat. Now, our working hypothesis is that a foam formulated with PNS-F, when applied as a thin mist directly into a fire, cools the fire and reacts with ions and radicals in the fire plasma. The foam droplets in the form of a thin mist have a high surface area to support reactions with ions and radicals. However, the foam applied as a thin mist collects on the surface to form a continuous blanket or barrier on the fuel to extinguish the fire and prevent rekindling. The composition will be formed with PNS-F, which is effective to apply in the form of a thin mist or foam stream. Examples show that PNS-F foam in the form of a thin mist is superior to PNS because of the foam protection properties.

[0063] FF Foam Discussion and Data:

[0064] Teflon is inert to combustion. The fluorine-containing surfactants in AFFF, such as fluorine-containing telomers, perfluorooctanoic acid (PFOA), or perfluorooctane sulfonic acid (PFOS), are nearly inert to combustion because these compounds are composed almost entirely of carbon-fluorine bonds similar to Teflon. AFFF foam is applied in a manner that forms a barrier on top of the fuel. Here, this resistance to ignition will be called re-ignition resistance.

[0065] Fluorine-free foams typically contain surfactants with organic components that burn in a strong fire. Here are some common examples of FF surfactants: soap (free fatty acid salts), fatty acid sulfonates, sodium lauryl sulfate, sodium lauryl ether sulfate, ethoxylated compounds (such as ethoxylated propylene glycol), lecithin, polygluconates (essentially a euphemism for short-chain starch). The most widely used surfactants are believed to be sodium lauryl ether sulfate (SLES), ammonium lauryl sulfate, ammonium laureth sulfate, sodium myristyl sulfate, and sodium myristyl ether sulfate. Widely used phosphate surfactants are mono- and di-alkyl phosphate ester salts with cations of sodium, potassium, lithium, and ammonium. The most widely used is potassium lauryl phosphate.

[0066] A surfactant is a compound that lowers the surface tension (or interfacial tension) between two liquids, between a gas and a liquid, or between a liquid and a solid. Surfactants can be used as detergents, wetting agents, emulsifiers, foaming agents, and dispersants. Here, a surfactant is a compound that lowers the surface tension (or interfacial tension).

[0067] Organic solvents can be included to improve the solubility of the surfactants, to improve the shelf life of the concentrate, and to stabilize the aqueous foam. Thickening agents can be used to increase the viscosity and stability of the foam. Other agents and additives known to those skilled in the art can be used. Surfactants are included in the foaming composition to facilitate the formation of foam upon aeration, to facilitate the diffusion of the effluent from the foaming composition into the liquid chemical as a vapor-tight aqueous foam, and to provide compatibility of the surfactant with seawater when required. Useful surfactants include water-soluble hydrocarbon surfactants and silicone surfactants, which can be nonionic, anionic, cationic, or amphoteric. When these surfactants are dissolved in water, negatively charged particles, i.e., anions, are produced. Particularly useful surfactants include anionic, amphoteric, or cationic hydrocarbon surfactants, such as anionic surfactants, which preferably have a carbon chain length comprising from about 6 to about 12 or up to 20 carbon atoms. As used herein, an amphoteric surfactant is a molecule that contains both positively charged atoms and negatively charged atoms. The surfactant molecule can include a polymeric component and can also include one or more counterions, such as sodium and ammonium, but the counterions are not considered to be one of the positively or negatively charged atoms that make the molecule an amphoteric surfactant. An amphoteric surfactant is a betaine surfactant, which means that the surfactant includes a betaine group. Amphotericism, in chemistry, refers to the reactivity of a substance with both acids and bases, acting as an acid in the presence of a base and as a base in the presence of an acid. Water is an example of an amphoteric substance. Silicone surfactants are a group of small molecule and high molecule surfactants that have found widespread application due to their unique properties. They consist of a polydimethylsiloxane (PDMS) hydrophobic group coupled to one or more polar groups. Silicone surfactants improve the quality of the foam by emulsifying incompatible formulation ingredients, reducing surface tension, facilitating bubble nucleation during mixing, stabilizing rising foam by reducing stress concentrations in thinning cell-walls, and by counteracting the defoaming effects of any solids added to or formed during the process. Silicone surfactants should facilitate the spreading of the foam to form a blanket over the flammable liquid. Saccharide surfactants, such as nonionic alkyl polyglycosides, can also be used in the composition. Organic solvents can be included in the foaming composition to facilitate the solubility of the surfactants, to improve the shelf life of the foaming composition for concentrated applications, to stabilize the foam, and in some cases to provide freeze protection.

[0068] FF surfactants are not considered to be flame retardants. Obviously, these surfactants have a high hydrocarbon content, which will become fuel if the surfactant is subjected to a strong fire and the water is protected from evaporation.

[0069] Organic solvents useful in the foaming composition include, but are not limited to, glycols and glycol ethers, including diethylene glycol n-butyl ether, dipropylene glycol n-propyl ether, hexylene glycol, ethylene glycol, dipropylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, propylene glycol, glycerol, polyethylene glycol (PEG), and sorbitol.

[0070] Thickeners are well known in the chemical and polymer arts, and include, among others, polyacrylamides, cellulose resins and functionalized cellulose resins, polyacrylic acids, polyethylene oxides, and the like. One class of thickeners that can be preferred for use in the foaming compositions and methods of the present application is the water-soluble polyhydroxy polymers, and especially the polysaccharides. Polysaccharides include a number of water-soluble organic polymers that can increase the thickness, viscosity, or stability of a foam composition. Preferred polysaccharide thickeners include polysaccharides having at least 100 sugar units or a number average molecular weight of at least 18,000. Specific examples of such preferred polysaccharides include xanthan gum, scleroglucan, heteropolysaccharide-7, locust bean gum, partially hydrolyzed starch, guar gum, and derivatives thereof. Examples of useful polysaccharides are described, for example, in U.S. Patents 4,060,489 and 4,149,599. These thickeners are typically present in the form of water-soluble solids (e.g., powders). Although they are soluble in water, in their powdered form they can and usually do contain small amounts of adventitious or inherent water that is absorbed or otherwise bound to the polysaccharide.

[0071] Xanthan gum is a microbial polysaccharide made from a fermentation of sugar by a bacterium called Xanthomonas campestris, which produces a gel that is dried and ground into a powder. The neutral-tasting gum is used as a powerful thickening, emulsifying, and stabilizing agent.

[0072] Kelco-Vis TM Diutan gum provides a new, multi-functional approach to formulating new high performance products with consistent quality and higher profitability. It is a very effective stabilizer with strong pseudoplasticity and other unique properties that are beneficial for a wide range of industrial applications, such as laundry liquids. Diutan gum is a polysaccharide that is used in applications that require very high suspension performance, such as cement, gypsum, mortar, agricultural chemical applications, and oil field drilling fluids, liquid detergents, and the like. Kelco-Care TMDiutan gum is a water-soluble biopolymer produced by fermentation that is specifically designed for use in cosmetics and other personal care applications. Kelco-Care TM Diutan gum has excellent thermal stability, is compatible with high levels of ethanol and polyols, and is readily biodegradable.

[0073] Another thickening agent that is particularly compatible with EAPPA is fumed silica. It will not fuel a strong fire.

[0074] All components used to make a Fluorine Free (FF) foam contain organic ingredients that will be consumed in a strong fire and the foam containing these compounds will break. Unlike foams made from fluorosurfactants, there is no contribution to the fire and the foam is not easily broken. The addition of a fire retardant such as EAPPA will help to resist the consumption of these organic ingredients in a fire. EAPPA does not evaporate, but rather becomes charred in the presence of a flame or high temperature. Therefore, the addition of an EAPPA solution to a FF foam will increase the resistance to water evaporation by providing some protection to the organic ingredients of the FF foam.

[0075] Plunging is the direct application of a fire retardant into the flame. In general, for flammable liquid fires, it is not recommended to use plunging because if water, dry chemical, carbon dioxide, or foam is used, it can splash the fire causing it to spread. Dry chemical, carbon dioxide, and foam extinguishers are applied at the bottom of flammable liquid fires. Foam should be sprayed gently from the edge of the flammable liquid fire to form a continuous blanket.

[0076] Low expansion foam is effective in controlling and extinguishing most flammable liquid ("Class B") fires. Low expansion foam is aerated to an expansion ratio between 2: 1 and 20: 1. Medium expansion foam has an expansion ratio between 20: 1 and 100: 1. High expansion foam refers to foam with an expansion ratio in excess of 100: 1. Most high expansion foam has an expansion ratio of 400: 1 to 1000: 1. Foam production requires an air aspirator or the addition of compressed air to a flow of aqueous liquid (e.g. water mixed with surfactant) that is passed very rapidly through the aspirator to form the foam. This device is commonly referred to as a Venturi Pump or Educator and is specialized for the production of foam. An educator is a device that uses the Venturi principle to introduce a foam concentrate into a water stream. Water entering the inlet of the educator is directed through a conical section and out through a small orifice (Venturi tube) into a larger chamber, creating a low pressure zone within the chamber. A metering valve is connected to the inlet of this chamber and when opened, allows the higher atmospheric pressure outside the chamber to push the foam concentrate into the chamber. The foam concentrate then mixes with the water coming out of the Venturi tube and the mixture flows out of the reverse conical section at the discharge end of the educator. Compressed air foam (CAF) involves the addition of compressed air to a solution of water and foam concentrate which is then discharged in large quantities from a hose. Foam cannons are used in the car wash industry to produce foam under pressure from a machine and utilize the Venturi principle.

[0077] Fluorine-free (FF) foam concentrates are complex mixtures of chemicals. Key ingredients are solvents, thickeners, water and surfactants. U.S. Patent 7,569,155 is one of the few patents that detail FFF compositions. One of the compositions contains 14 ingredients, all of which must perform a certain function: water, diethylene glycol monobutyl ether, xanthan gum, starch, diethanol amine lauryl sulfate, sodium decyl ethoxy sulfate, cocamido propyl betaine, cocamido propyl hydroxysultaine, carbonized sugar mixture, alkyl polyglycoside, dextrose, triethanol amine, biocide and benzotriazole. Those familiar with FFF will undoubtedly add more ingredients such as these to our base composition to achieve particularly important commercial performance.

[0078] The military MILSPEC test (MIL-F-24385F) is conducted on a fire consisting of 10 gallons of E0 gasoline in a 28 square foot circular tank and 15 gallons of E0 gasoline in a 50 square foot circular tank, and also contains one inch of water. The 10 gallons of gasoline in the 28 square foot tank will form a layer that is only 0.57 inches thick. Fire performance is defined more specifically by U.S. MilSpec Mil-F-24385F, which can be the most stringent compared to other performance standards used in civilian applications (e.g., International Civil Aviation Organization (ICAO), Underwriters Laboratories Inc. (UL)) for AFFF used in DOD fire fighting applications. The test procedure also specifies a foam venturi nozzle. This nozzle will be referred to as the MILSPEC nozzle and is used in some of the tests presented herein. One of the tests conducted according to U.S. MilSpec is the extinguishment test, which specifies a gasoline pool fire (28 square feet) that is 6 feet in diameter to be extinguished in less than 30 seconds at a rate of 2 GPM. After the foam is sprayed for 90 seconds, a one foot diameter pan containing one gallon of E0 gasoline is placed in the center of the tank. Then, for backdraft resistance, the time before the gasoline fumes from the foam barrier escape to ignite half the tank is measured. The flame produced by the one foot diameter pan burning one gallon of gas degrades the foam, and thus the fumes aid combustion. The flame from the pan is initially small, but as the fumes under the foam aid combustion, the flame gets higher and hotter. The test passes if the time to burn half the tank is less than 360 seconds. This test is referred to as backburn because for a 28 square foot test, the foam layer needs to protect for 6 minutes from being completely re-ignited. The U.S. Congress has mandated the manufacture of a FF foam to replace the current fluorine-containing foam that passes this MILSPEC test, and this is the goal of this work.

[0079] A pressure washer can be used to produce foam as described in PCT / US20 / 52061. Instead of a flat spray tip, a foam lance is used. A foam lance is a device consisting of a venturi connected to a chamber containing a wire mesh screen that is 0.61” in diameter and 0.41” in height. Thus, the venturi mixes air and the foam solution and then the air and solution are thoroughly mixed by the wire mesh screen, producing a very uniform foam, like shaving cream. The MTM Hydro PF22 Professional Foam Lance sold by Amazon.com is a good choice for forming foam with a pressure washer. Professional auto detailers use pressure washers with foam lances to wash cars. The foam lance converts soapy water into foam that is used to wash the car. One of the highest rated foam lances is the TORQ snow cannon EQP 321, which is used in the text and is available from www.chemicalguys.com.

[0080] The MILSPEC nozzle and the foam lance are similar in that they both have a venturi design. They differ in that the dispersion cone. The foam lance has a 3 / 8” NPT feed line, while the MILSPEC has a ½” NPT feed line. Both nozzles force the feed solution through a narrow passage into a much larger passage of intake air, and then through a smaller passage. For the MILSPEC nozzle, the air and solution are then mixed together in the smaller passage to form foam by a dispersion cone having a 1 1 / 8” long, ¼” diameter circular tip. For the foam lance, a 0.41” thick wire mesh screen is placed in the smaller passage whereby the foam and air are mixed and the foam is expelled that looks like shaving cream. The foam from the MILSPEC nozzle is much coarser than the foam from the foam lance. The MILSPEC nozzle can be easily modified to perform like the foam lance by replacing the dispersion cone with a wire mesh screen having a thickness of at least 0.2” (more preferably 0.41”).

[0081] It is very important that the foam gently falls on the gasoline so as not to substantially disturb the surface of the burning liquid. The foam near the surface of the burning gasoline has a high surface area that reacts with the ions and free radicals that are streaming from the surface, thereby extinguishing the flame.

[0082] The commercial FF foam used herein is National Foam Universal Green 3% produced by National Foam of West Chester, PA, and re-healing RF3 3x6 ATC (Solberg ATC) and Solberg RF3 provided by Perimeter Solutions of Clayton, MO.

[0083] To produce a mist in most cases, it is preferred to use a flat fan nozzle that produces a fan shaped mist. The fan shaped mist is swung into the fire and moved from one side to the other to interact with the fire. It is preferred to direct the mist down toward the fire surface and to maintain a distance above the surface so that liquid splatter does not occur. The amount of mist needs to be sufficient to extinguish the fire and not re-ignite the fire. The volume of mist and area covered needs to be such that the fuel on one side of the fire does not re-ignite before the fan shaped mist reaches the other side. If the amount of mist is insufficient, a boom containing several flat fan nozzles and possibly a higher pressure pump can be used to obtain additional mist per unit time. Hundreds of different nozzles are available for agriculture and are directly applicable herein.

[0084] After multiple tests with flat fan nozzles, it was found that a hollow cone nozzle performed better than the flat fan nozzles because the mist fell more gently on the surface.

[0085] Mist can be formed at low pressures but only a small amount of mist can be produced. In application PCT / US / 20 / 52061, there is a lengthy discussion of mist or PNS containing foam extinguishment with PNS solution. There is no disclosure of extinguishment with foam converted to mist. Surprisingly, a foam composition can be injected through a mist nozzle and form a mist without breaking up the foam bubbles. It was hypothesized that the very small orifice of a mist nozzle would break up the foam bubbles by compression. In fact, it will now be shown that a foam mist can be formed with an expansion ratio of at least 5. First, a Solberg ATC foam solution with a concentration of 6% was injected through a Torq foam cannon. The foam was found to have an expansion ratio of about 8.5. The MILSPEC test requires an expansion ratio of at least 5. The foam cannon was modified by removing the plastic guard and welding a 3 / 4 inch copper fitting to the tip of the foam cannon. The fitting was used to connect a boom with three to five spray tips from Teejet Company (6798 Danboro Ct. NE, Rockford, MI 49341). The boom containing 5 nozzles was connected to the end of the Torq snow cannon in a rectangular pattern. The expansion ratio of the mist leaving the nozzles was measured to be 8.2 for nozzle 11015, 7.2 for nozzle 11008, and 6.2 for nozzle 8005 compared to the expansion ratio of 8.5 without the boom. The nozzles did inhibit a small amount of Solberg ATC foam expansion but were acceptable for forming a foam that would easily float above the gasoline. Thus, even for a fine mist such as nozzle 8005, the foam bubbles formed in the foam cannon were able to exist as they left the nozzle.

[0086] The Solberg ATC 3% foam solution described above was now applied to a 28 square foot box of 5 gallons of gasoline. The foam could not extinguish the gasoline fire in 90 seconds with the Torq foam cannon. For the next test, a boom with 5 11015 nozzles was attached to the end of the foam cannon to create a thin mist of foam. The thin mist of Solberg ATC foam applied extinguished the 28 square foot 5 gallon gasoline fire in 55 seconds (on one trial) and 65 seconds (on the second trial) respectively. The thin mist sprayed with the boom provided a greater coverage area to overcome the poor coefficient of expansion of the FF foam. The thin mist was applied at a considerable pressure that acted on the surface and cooled it. This thin mist, which was much lighter than the gasoline, quickly formed a protective barrier on the surface that prevented reignition even if a bubble broke the surface of the fuel. Therefore, the thin mist of foam is a simple way to improve the performance of FF foam. AFFF foam sprayed as a thin mist will also be more effective if sprayed as a thin mist with a large coverage area. AFFF can dry out in a high temperature fire at which point the fluorinated compounds will break down and form free radicals that react with the flame and help extinguish the fire. This is a key performance that FFF foam does not have. For this reason, our goal is to add FR behavior to FFF.

[0087] In the MILSPEC test, the foam needs to spread rapidly over the gasoline as the foam is applied. Therefore, AFFF, which is primarily composed of carbon-fluorine bonds like Teflon, will be particularly prone to spread in a fire driven by thermal energy. Another overlooked performance of AFFF foam is that they are prone to spread in a fire because they react less with neighboring chains. FF foam, which is composed of very sticky FF surfactant bonds, is more difficult to excite to spread and therefore has a poor coefficient of expansion. Application as a thin mist over a large area helps to overcome the inherent problem of spreading over a flame, especially when using nozzles with a spray angle of 110° as now.

[0088] Now, more evidence provides the advantages of forming a foam solution with PNS to form a foam and then converting it to a thin mist. The foam in this specification is formed by adding air to a foam solution (water and foam concentrate) using an eductor or air aspirating nozzle at a pressure of at least 100 PSI. In the previous example, a foam cannon, a type of air aspirating nozzle, was used to create a foam from a foam solution containing 3% to 6% foam concentrate and water. The advantage of this method is that the thin mist created stops all combustion and the foam agglomerates on the surface of the water to form a coating on top of the fuel and provides protection from reignition.

[0089] One important property of the PNS solution is that PNS reacts violently with sulfate and phosphate surfactants. This direct reaction of the fire retardant with the surfactant is not disclosed in PCT / US20 / 52061. Mixing SLES at a concentration of 27% with the PNS solution produces a gel-like viscous solution. When SLES is mixed directly with a foam concentrate such as Solberg ATC, the reaction is much more benign.

[0090] The SLES surfactant used in all examples was SLES at a concentration of 27% purchased from the website www.chemicalstore.com .

[0091] Example 1 Adding DETAPPA to SLES foam: 400g of DETAPPA-FS at a concentration of 67% was mixed together with 8g of xanthan gum in a blender to make a foam solution. Then, 400g of SLES at a concentration of 27% was added and the solution became very viscous due to the interaction of SLES with the DETAPPA-FS and was mixed by hand. This solution was then added to 4000g of water and mixed for about 5 minutes at which time 140g of ethylene glycol butyl ether was added and the viscosity dropped significantly. After about 1 hour, this solution was added to 9000g of water and stirred with a spatula. This solution was then pumped into a 20 gallon standard water tank with a bladder. An air compressor was then used to pump air into the bladder and mix with the solution with a final pressure of 75 PSI. The tank was then connected to a 4000 PSI Simpson pressure washer to be used as the liquid feed for the pressure washer. A Torq foam cannon modified with a boom containing 4 nozzles (size 11020) was connected to a 50 foot 3 / 8 inch hose from the pressure washer. The foam coming out of the foam cannon was about 120g / 800ml (6.6 times expansion). The foam coming out of the boom with 4 nozzles was about 165g / 800ml (4.9 times expansion) indicating that the additional step of forming a mist reduced the expansion rate. A 28 square foot tank was filled with 5 gallons of water and then 5 gallons of E10 gasoline was added. The gasoline was ignited and after 10 seconds the mist of foam was applied. Surprisingly, the fire was extinguished in 30 seconds and a layer of foam formed on the surface. The misting was continued for 60 seconds and the layer of foam thickened. After 6 minutes, a torch was applied to the surface of the layer of foam. The gasoline under the layer of foam was not ignited indicating that it had significant backdraft performance. This result was superior to the results of applying a stream of foam from a foam cannon with an extinguishing time of over 60 seconds. The mist appears to react with the gas plasma and cool the flame because the test person felt that the heat emitted was greatly reduced when the mist was applied.

[0092] Example 2: The same procedure was repeated with the exception that 12 g of KELCO-VIS diutan from CP Kelco (Huber Corporation) was used in place of the 8 g of xanthan gum. The burn time was 33 seconds. Diutan is a substitute for xanthan gum.

[0093] Next, a thin mist of 45% DETAPPA-FS solution was applied to a 5 gallon gasoline fire in a 28 square foot tank as a foam / thin mist example. The PNS thin mist was unable to extinguish the fire in 60 seconds, at which time the tank went dry. The thin mist was more effective at extinguishing the fire, but was not effective at cooling the sides of the tank, and the fire was quickly re-ignited after being extinguished. This example illustrates the importance of foam in extinguishing fuel tank fires. Surfactants are critical to foaming.

[0094] Commercial FF foams contain surfactants that are not flame retardants. A flame retardant such as PNS can be added to the FF foam body, thereby reducing foaming. These surfactants can be replaced with a new surfactant, PNS-F, which is also a flame retardant, which is now described. The surfactant and flame retardant PNS can also be prepared simultaneously to obtain a compound that is both a flame retardant and a foaming agent surfactant. PNS-F can be added without reducing the expansion ratio.

[0095] Phosphates such as lauryl phosphate are not water soluble. One of the drawbacks of EAPPA is that they are water soluble, thus limiting their usefulness in forming flame retardant polymer compositions for wire and cable applications. It would therefore be useful to have some of the bonds in the polyphosphoric acid form ester bonds with lauryl alcohol and then react with ethylene amine.

[0096] Complex alkyl sulfates are made by reacting a fatty alcohol, an ethoxylated alcohol, or an ethoxylated phenol with sulfuric acid. Lauryl ether sulfate (LES) is made by ethoxylating dodecanol and then reacting with sulfuric acid.

[0097] Soap applications typically use glycol ethers as couplers to keep dirt suspended by making hydrophobic oils and dirt water compatible. This compatibility can be the reason for the FF foam with ethylene glycol. Glycol ethers used as solvents (co-solvents) include any reaction product of ethylene oxide or propylene oxide with some alcohols including methanol, ethanol, propanol, butanol, hexanol. These can include any of the following ethylene oxide based materials such as: 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 these can include any of the following propylene oxide based materials such as: 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.

[0098] The product glycol ether EB (ethylene glycol monobutyl ether) was obtained from Chemistry storcom. Silwet L-77 was obtained from DeWolf chemical distributor (dewolfchem.com). Silwet L-77 is a non-ionic silicone surfactant copolymer that has enhanced wetting and spreading properties when used in aqueous sprays. It can also be used as a wetting agent because it can reduce the surface tension of aqueous solutions. Momentive® is a registered trademark of Momentive.

[0099] Ethoxylated alcohol phosphates are commercially available. Of the many products available, three were chosen here as typical products: Crodafos T6A from Croda Inc., Stepfac 8180 and 8182 from Stepan Corparation, Northfield, IL, 60093. www.Crodaindustrialchemicals.com Crodafos T6A from Croda Inc. is described as a polyethylene glycol monododecyl ether phosphate (or phosphate ester of an alkyl polyethoxy ethanol) containing 3 moles of EO, 42% monoester and 53% diester, dispersible in water. Stepfac 8180 and 8182 from Stepan Corparation, Northfield, IL, 60093. Stepfac 8182 contains 12 moles of EO, 45% monoester and 37% diester, soluble in water. Stepfac 8181 contains 6 moles of EO, dispersible in water. The pH range is 2-3. T6A is a tridecanol phosphate with 6 moles of EO. These products can also contain about 1% phosphoric acid. Because of the presence of EO, they are more water soluble than lauryl phosphate. These phosphates have emulsifier, detergent, hydrotrope, corrosion inhibitor, wetting agent, solubilizer, and dispersant properties. We will illustrate that such phosphates react with ethylene amines (such as DETA) to produce compounds with flame retardant properties as well as foaming properties. Lauryl phosphate is not water soluble, but is hygroscopic in hot humid air, probably due to impurities. LP has an acidic pH, and the acid tends to absorb water.

[0100] Stepan Company offers a series of ethoxylated fatty alcohols Makon DA series, or ACME HARDESTY Company (Blue Bell, PA) produces a product called lauryl alcohol ethoxylate 2 moles of EO and 9 moles of EO, which will be used herein. Stepan Company offers TD-6 contains 6 ethylene oxides. Makon UD series is a C11 branched alcohol ethoxylate. Makon DA-4 (4EO) is dispersible in water, Makon DA 6 (6EO) and 9 (9EO) are soluble in water. Makon UD 5 (5EO) is dispersible in water and soluble at concentrations below 10%. Makon UD 6 (6EO) and 8 (8EO) are soluble in water at concentrations greater than 10%. Makon TD 3 (3EO) is not soluble in water, TD 6 (6EO) is dispersible in water, TD 8 (8EO), 9, 12, 18 (18EO) are soluble in water. Thus, as the amount of EO increases, the solubility in water increases. Solubility also depends on the specific fatty alcohol that is ethoxylated. The TD series is tridecanol, the UD series is a C11 branched alcohol ethoxylate, and the DA series is a C10 isodecanol ethoxylate.

[0101] Kelco-Care TM Diutan Gum is a water-soluble biopolymer produced by fermentation that is specifically designed for use in cosmetics and other personal care applications. Kelco-Care TM Diutan Gum has excellent thermal stability, is compatible with high concentrations of ethanol and polyols, and is readily biodegradable. TM Diutan Gum is a water-soluble biopolymer produced by fermentation that is specifically designed for use in cosmetics and other personal care applications. Kelco-Care TM Diutan Gum has excellent thermal stability, is compatible with high concentrations of ethanol and polyols, and is readily biodegradable.

[0102] Dodecyl Phosphate (CA-PE) was obtained from Boc Sciences, website www.bocsci.com It is not soluble in water. The terms lauryl and dodecyl are used interchangeably. The process of forming the salt of dodecyl phosphate was demonstrated by the formation of dodecyl phosphate and potassium dodecyl phosphate according to US 6,262,130.

[0103] To form DETA lauryl phosphate, the lauryl phosphate was first melted and then DETA was slowly added until the pH reached 5 to 8. A foamy sample of DETA LP was formed by dissolving 160 g of LP in 3600 g of hot water. Then 4 g of xanthan gum and 34 g of glycol ether EB were added. The pH of the solution was 2. After adding 52 g of DETA, the pH was 6.7. The expansion of this composition in a pressure washer was 5.3, while in an Amerex foam extinguisher it was only 2.7. If the foam solution is sprayed as a fine mist, much better results are obtained.

[0104] Diethylene triamine phosphate is a good fire retardant, and this compound expands when it encounters fire. Ammonium phosphate does not expand in fire. It was found that DETA lauryl phosphate (DETA LP) also expands.

[0105] The solution containing DETA LP was converted to a foam in a blender and 75 g of the foam was placed in a high wall pan. A second foam sample was also formed from 6% of the Solberg ATC solution. Both were placed in a propane grill preheated to 600°F. The heat caused the Solberg ATC foam to expand and almost fill the pan in 2 minutes. The Solberg ATC started to break up at 3 minutes. The DETA LP expanded to fill the pan at 2 minutes, but at 3 minutes it continued to expand further and overflow the walls of the pan. This was interpreted to mean that the DETA LP foam was significantly better than the Solberg ATC without the rapid break up of the bubbles. This behavior was expected because DETA is a crosslinker with special properties with epoxy resins. It was found that the foam containing DETA LP had significantly better heat resistance.

[0106] The amount of solution remaining in the pan for the Solberg ATC was 23% compared to 43% for the DETA LP, even though some of the DETA LP foam escaped from the sides.

[0107] Synthesis of Diethylene triamine lauryl phosphate (DETA LP) aqueous solution:

[0108] Into a blender was added 52 g of dodecyl (lauryl) phosphate (LP), 0.5 g of xanthan gum, 3 g of glycol ether EB, and 2100 g of hot water (60 °C) and mixed to suspend the LP in the water. Next, the solution from the blender was added to a mixer and 9 g of DETA was added. Grade 115% polyphosphoric acid was added to lower the solution pH to about 6.

[0109] Some of the DETA LP solution was added to a metal container to form a layer about ½ inch deep. A torch was applied and after the water was removed by the torch a layer formed on the surface. Eventually, as the liquid evaporated an expanding char formed indicating that this compound has fire retardant properties.

[0110] About 4 gallons of the DETA LP solution was added to a 20 gallon water tank with a bladder. The solution in the tank was pressurized to 90 PSI. The tank was connected to a 4000 PSI Simpson pressure washer. The hose was fitted with a Torq TM Foam Cannon. The foam cannon was fitted with a linear array of four foam nozzles (Teejet TFVS10) spaced about 4 inches apart. The device was found to form foam with an expansion ratio of 7-8 demonstrating the surfactant properties of DETA LP. It will be shown later that with MILSPEC nozzles the expansion ratio is less than 5.

[0111] To test the foam extinguishing properties, the foam formulation was applied to a 28 square foot fire containing 5 gallons of standard gasoline containing a 10% content of ethanol (E10 gasoline). If the nozzles were Teejet 8003 which jet a fine mist of foam, the fire was extinguished in 30-40 seconds. The fine mist nozzles reduced the expansion ratio to about 3-4. Apparently, the fine mist of foam reacts with the flame plasma. The spraying was continued for a total of 90 seconds. The layer of foam formed on the surface had a long life of at least 60 minutes. A torch applied to the surface of the foam on top of the E10 gasoline did not ignite the gasoline. This behavior demonstrates backdraft protection, i.e. the gasoline will not be re-ignited, which is a key requirement of the MILSPEC test. However, if allowed to stand for a month, the DETA LP has a tendency to drip from the solution, which requires a better candidate for foam application. It will be found that ethoxylation of the alcohol enables the solution to have a long life without dripping. A non-aqueous form of this compound would be better added to polymeric compositions where low water solubility is preferred.

[0112] The same procedure can be used to synthesize a lauryl sulfate solution of EA. Other ratios of acid to base and other concentrations can also be employed. It is also desirable to form a solution by heating PPA and LP together to react and then adding EA.

[0113] Synthesis procedure for EA lauryl phosphate (CAPE) - PPA:

[0114] According to the application, lauryl phosphate and PPA are added in the given ratio to a reactor which is heated to a temperature at which the lauryl phosphate is easily melted and easily stirred so that the product can be extracted. Ethylene amine such as DETA is started and mixing is started. The reactor temperature can need to be raised to melt the EA lauryl phosphate product and to be easily stirred. When finished, the product, EA lauryl phosphate-PPA, is collected. Other ratios of acid to base can also be used.

[0115] The definition of the term melting temperature must be expanded for the compounds of the present application. Some phosphate esters and polyphosphate esters can not have a melting temperature. These compositions soften with temperature and at some point are easily stirred. They tend to be thixotropic. Since these compounds can be made in a kettle, the temperature of the kettle must be such that the compound can be easily extracted, which requires the temperature at which the product flows. The final temperature must be the temperature at which the composition flows so that it can be extracted. It is important that mixing not be stopped at a given temperature before the product is extracted because it is difficult to restart mixing. Therefore, this temperature will be called the flow temperature. For compounds made in an aqueous phase or a mixed aqueous-organic solvent, the temperature must be such that the parent compound dissolves, which is usually a complex alkyl phosphate solution or a sulfate. This temperature is called the solution temperature.

[0116] Synthesis of ethylene amine lauryl phosphate and ethylene amine polyphosphate (CAPE-PPA) mixtures:

[0117] Another method is demonstrated by forming an aqueous solution of EALP doped with EAPPA. The specific example will use DETA. 53.3 g of dodecyl (lauryl) phosphate (LP), 0.5 g of xanthan gum, 3 g of glycol ether EB, and 2100 g of hot water (60-80 °C) are added to a blender and mixed to dissolve / suspend the LP in the water. Next, the solution in the blender is added to a mixer, and 15 g of DETA is added to obtain a pH of about 8.5-9. Then, an additional 3 g of DETA is neutralized by adding about 6.7 g of grade 115% polyphosphoric acid to reduce the pH to about 6-7. Thus, this method includes making a solution of an excess of EA to EA complex alkyl phosphate solution in hot water, and then adding polyphosphoric acid to neutralize the excess EA. Alternatively, this method includes adding polyphosphoric acid to hot water, then adding the complex alkyl phosphate, and then adding EA to obtain a pH of about 6-7. The same procedure applies to other complex alkyl sulfates.

[0118] In a similar manner, DETALS (DETA lauryl sulfate) and DETALE (DETA lauryl ether sulfate) can be made with a waterless method. The water-containing method will use lauryl sulfate (LS) and EA or lauryl ether sulfate (LES) and EA.

[0119] Example EA-(CAPE-PPA) EAPPA and DETA PPA mixture

[0120] Forty-eight grams of LP and 48 g of 115% PPA were melted together in a stainless steel pressure cooker to form a clear solution which we named DETAPPA / LP. The ester linkages were pre-bound in the LP. Then 34 g of DETA was added so there was almost no outgassing. After two weeks in the humid hot air it did not become sticky. Although the LP did not dissolve, a sample of the LP that was left in the air at the same time became very sticky. A large chunk of the DETAPPA left in the air at the same time liquefied completely dissolving. A second DETAPPA / LP sample was formed from 25 g of LP and 54 g of PPA and flexible 34 DETA. As with the first two samples, left in the humid hot air, the sample was slightly sticky but did not liquefy. Thus, these experiments give a clear pathway to forming a polymer sample that has greatly reduced humidity sensitivity that is required for a polymer.

[0121] Example CA-PPA: EAPPA and DETA ethoxylated tridecanol polyphosphate mixture formation

[0122] At room temperature, 25 g of Makon TD3 and 48 g of 115% PPA were mixed together in a stainless steel pressure cooker to form a clear solution of ethoxylated tridecanol polyphosphate solution (complex alkyl polyphosphate solution). There was no need to heat to 400°F to make the reaction go. It was necessary to heat the reaction vessel to a temperature of 400°F in order to extract the product by pouring it out. The pot got quite hot indicating that there was a reaction. The solubility and reaction were a bit surprising since Makon TD3 is not soluble in water. Then 34 g of DETA was added so there was almost no outgassing. A flexible solid was formed. It did get a bit sticky after two weeks in the humid hot air but much more slowly than DETAPPA. This moisture resistant composition has utility in flame retardant polymers compared to EAPPA.

[0123] No phosphorous pentoxide is used. To form the ethoxylated alcohol polyphosphate solution (CA-PPA), first pre-heat the reactor (e.g. 10 L Henschel mixer) to a temperature of at least 100°C but less than 220°C. Add about 1600 g of 115% polyphosphoric acid and stir. Determine the percentage of the final ingredients that should react with the complex alkyl compound (such as Makon TD3). Then, add Makon TD3 at a concentration that should result in the correct proportion in the CA-PPA. Depending on the application, other ethoxylated alcohols can be added. Continue mixing until the reaction is complete and a solution is formed. Then add DETA to bring the pH to 3-9. A pH of 9 indicates that additional DETA was added. This process can also be done with other ethoxylated alcohols or with other fatty alcohols. This process will be defined as a method to make ethylene amine ethoxylated complex alkyl polyphosphates with EAPPA in any desired proportion depending on the application. The ethoxylated alcohol can react with only the phosphoric acid component in the polyphosphoric acid to form an ester. The long chain PPA appears to have very few bonds that can form an ester.

[0124] Example 4 (CA-PPA viscosity): The reaction of PPA and complex alkyl is further investigated in the following examples. For this example, Makon DA-9 from Stepan Company (primarily a C10 alcohol) will be combined with 115% PPA at a temperature of 400°F. At a ratio of 200 g Makon DA 9 to 75 g PPA, the viscosity is significantly higher than the viscosity of PPA or Makon DA9 by itself. At a ratio of 175 g Makon DA9 to 100 g PPA, the viscosity is increased over the previous example. At a ratio of 150 g Makon DA9 to 100 g PPA, the viscosity is further increased. At a ratio of 125 g Makon DA9 to 150 g PPA, the viscosity is still high and now the enhanced color is a reddish color. Even with the increased viscosity, the viscous solutions are all clear. These results indicate a strong bonding between the two components. There is no evidence of separation in an aqueous solution. This behavior is similar to the behavior of hydrophilic fumed silica dissolved in PPA. Mixing at room temperature cannot successfully make these two ingredients form a clear brown / red solution because it happens easily at 400°F. The molecular weight of Makon DA 9 is approximately 550 depending on grade and the molecular weight of PPA is in the range of 85 to 90. These samples contain more moles of PPA compared to Makon DA 9. The weight of all samples is the same. The amount of EA used to neutralize to a pH of neutral increases as expected with the amount of PPA relative to Makon DA9.

[0125] Solvation refers to the process of chemical association between solute molecules and solvent molecules. The ethoxylated complex alkyl fatty alcohol can be solvating the PPA, particularly the long chain portion, rather than the ester in form. However, we define the solvated acid as the solution for the purposes of defining the composition of interest. The solvation process does not appear to have any reversal, even after reaction with ethylene amine, the alcohol remains associated with the acid. With the orthophosphoric acid content of 115% PPA, ester formation is possible. For 105% PPA with an orthophosphoric acid content closer to 50%, this effect is much greater.

[0126] These samples are foam samples produced in a very similar process.

[0127] Example 1 CA-PPA: Formation of DETA ethoxylated tridecanol polyphosphate: The first step is to mix 150 g of 115% PPA and 360 g of Makon TD3. A clear solution is formed, releasing a significant amount of heat, and the reaction occurs. The clear solution is heated at 60-80°C for 5 minutes to ensure the reaction is complete. 192 g of this solution is added to 2100 g of hot water (about 80°C) in a blender. 11 g of ethylene glycol EB is added and the solution is mixed. Next, the contents of the blender are added to a standard dough mixer. The last step is to add 60 g of DETA. Four batches are prepared, with a pH of 8.2, indicating an excess of DETA. DETA is a crosslinker, and for this reason, additional DETA is added, as we expect to make a foam blanket to extinguish fires. Some of the solution is placed in a blender and mixed. A foam is prepared with an expansion ratio of 5. The solution is also added to a tank pressurized to 50 PSI and connected to a 4000 PSI Simpson pressure washer. The pressure washer hose is connected to a Torq foam cannon. The foam cannon is connected with 10 Teejet fine mist 8003s in a rectangular bar configuration. The foam produced in this manner has an expansion ratio of 6.4, which is excellent considering the fine mist produced.

[0128] Example 2 CA-PPA: Formation of Foam Concentrate: For practical use, it is necessary to form a foam concentrate. 30 g of the above composition (150 g 115% PPA and 360 g Makon TD3) was mixed with 9.4 g DETA in a sealed pressure cooker. The cooker was heated to 80°C to ensure complete reaction. The cooker was opened and the ingredients were mixed thoroughly. A soft solid mass was formed. 30 g of this solid DETA ethoxylated fatty alcohol polyphosphates was mixed with 350 g water and 2 g glycol ether EB in a blender. After several trials, the foam formed had an expansion of 4.5 to 5. Thus, this neat 100% product can be mixed with water when needed in a fire. It can also be dissolved in water with a few percent of water, for example, 1 : 1 by weight. Thus, the neat product or concentrated aqueous form can be practically shipped to the fire scene for use by the fire department.

[0129] Example 3 CA-PPA: 45 g of 115% PPA was added to 135 g of ACME HARDESTY lauryl alcohol ethoxylate 2 mol EO. Both did not react after constant mixing. However, heating in a closed pressure cooker at about 400 F for 5 minutes did initiate the reaction. This was done again to complete the reaction to form a purple syrup-like solution that was clear in a thin coating. The product was allowed to cool to a gel. This product will be called lauryl ether polyphosphate solution with two moles of EO. 27.3 g of this product was mixed with 1.5 g of glycol ether and 300 g of water in a blender to form a foam. 8.6 g of DETA was added to the blender, but the amount of foam remained about the same. The pH was 9.4 and the expansion was 4.85. The next sample contained 27.3 g of the product, 1.5 g of glycol ether, 300 g of water and 6.0 DETA. The addition of DETA did not change the amount of foam. The expansion was 5.0 and the pH was 7.0. The foam was heated with a torch and it took 3 minutes to convert 45 g of foam to char. Thus, this new compound has both foaming agent properties and fire retardancy. Thus, the product is defined as the process of reacting ethoxylated fatty alcohol with PPA in a closed vessel at temperatures below 450 F and then neutralizing with DETA. To make a foam concentrate, the glycol ether and water are added before the DETA. The ethoxylated fatty alcohol appears to react more easily with PPA when the alcohol chain is longer.

[0130] Example 4 DEEA ethoxylated fatty alcohol phosphate (CAPE): For this example, 192 g Stepfac 8180 (contains a significant amount of di-esters) was added to a blender containing hot water at a temperature of 60-80 °C. Also added was 11 g of ethylene glycol EB and the solution was mixed. Next, the contents of the blender were added to a standard dough mixer. The final step was to add 30 g of DEEA. Four batches were made with a pH of 8.0, indicating an excess of DEEA. The solution was also added to a tank pressurized to 50 PSI and connected to a Simpson pressure washer at 4000 PSI. The pressure washer hose was connected to a Torq foam cannon. The foam cannon was connected with 10 Teejet fine mist 8003 nozzles in a rectangular bar configuration. The foam produced in this manner had an expansion of 6.2, which is excellent considering the fine mist produced.

[0131] Example 5 DEEA LP: A third sample was prepared by adding 120 g of LP to 2100 g of hot water (60-80 °C) in a blender with 11 g of glycol ether EB. The solution was added to a dough mixer. While stirring, 30 g of DEEA was added. Four batches were made with a pH of 7.9, indicating an excess of DEEA. The solution was also added to a tank pressurized to 50 PSI and connected to a Simpson pressure washer at 4000 PSI. The pressure washer hose was connected to a Torq foam cannon. The foam cannon was connected with 10 Teejet fine mist 8003 nozzles in a rectangular bar configuration. The foam produced in this manner had an expansion of 7.7, which is excellent considering the fine mist produced. It is important to note that only 30 g of DEEA was used, whereas the earlier example of DEEA used 60 g of DEEA, which further indicates the universality of mono-esters.

[0132] Example 6 DETA ethoxylated alcohol sulfate: A fourth sample was prepared by mixing 150 g of 96% concentration sulfuric acid and 360 g of Makon TD3. A clear solution was formed, releasing a significant amount of heat, and the reaction occurred at room temperature. The clear solution was heated at 60-80°C for 5 minutes to ensure the reaction was complete, and the color changed to purple but was still very clear. 192 g of this solution was added to 2100 g of hot water (about 80°C) in a blender. 11 g of ethylene glycol EB was added and the solution was mixed. Next, the contents of the blender were added to a standard dough mixer. The last step was to add 60 g of DETA, which had a pH of 9.1. The next batch was prepared with 55 g of DETA, which had a pH of 8.7, indicating an excess of DETA. DETA is a crosslinker, and for this reason, additional DETA was added because we were expecting to make a foam blanket to extinguish a fire. Some of the solution was placed in a blender and mixed. A foam was prepared with an expansion ratio of 3.3. The solution was also added to a tank pressurized to 50 PSI and connected to a 4000 PSI Simpson pressure washer. The pressure washer hose was connected to a Torq foam cannon. The foam cannon was connected with 10 Teejet fine mist 8003s in a rectangular bar configuration. The foam produced in this manner had an expansion ratio of 5.3, which was excellent considering the fine mist produced by the fine mist nozzles. This foam appeared to not form a swollen char as much as the composition when subjected to a propane torch.

[0133] Similarly, ethoxylated complex alkyl fatty alcohols can be reacted with sulfonic acids to form esters. Then, ethylene amines are reacted with the ethoxylated complex alkyl fatty alcohol sulfonic acid esters. These sulfonic acids are not readily available, so no examples will be provided.

[0134] Example 7 CA-PPA: Method to prepare 50% concentration of PNS-F for wildfire control:

[0135] In a glass blender, 7.5 g of complex alkyl Makon DA-9 and 160 g of 115% PPA were added and mixed at 400°F to form a slightly colored clear solution (CA-PPA). Then, 265 g of water was added and mixed. A copper tube was then inserted into a small hole drilled into the lid of the blender. While mixing at the lowest speed, 91 g of DETA was added to the 1 / 8 inch internal diameter tube, 2 g at a time. It took about 7 minutes to add the DETA. The solution had a pH of 5.7. The temperature of the solution was 155°F due to the exothermic reaction. There was no noticeable steam leak from the blender. Although the hot air in the blender created some pressure, the accumulated pressure did not open the lid.

[0136] A freshly prepared solution was thinly applied to a 12-inch long, ¼-inch diameter wooden dowel. The dowel was hung vertically from a supported propane torch so that the flame was directed vertically at the dowel. The tip of the torch was 2 inches from the top of the dowel. The torch was ignited. The dowel burned a little at the bottom, about 4 inches burned. The flame was small and the heat released was very little. No ember formed, indicating no infrared radiation. Once the torch was stopped, the burned portion of the dowel cooled in a few seconds. In comparison, an uncoated dowel burned in the same manner very quickly, leaving an ember about 12 inches long that broke off quickly. The ember continued to radiate infrared radiation and was hot to the touch. Clearly, an analogy can be made between the difference between an incandescent light bulb and an LED light bulb. The visible light is similar. But the incandescent light bulb is too hot to touch, while the LED light bulb can be easily touched. Thus, the uncoated dowel, when burning, radiates heat that can ignite adjacent fuel. The coated dowel, when burning, does not radiate long wavelength heat, and once the heat dissipates, the dowel is no longer hot. Thus, the fuel coated with PNS-F or PNS with the addition of foam is deprived of the ability to ignite adjacent fuel, and this is the key to stopping wildfires. The addition of the foaming function to PNS improves the formation of a thin film so that the solution applied to the surface does not drip. The PNS-F foam solution is more likely to form a thin film that does not drip.

[0137] Another method of making PNS at a 50% concentration. This method includes using the primary ingredients 115% PPA and DETA without external heating. In a glass blender, add 265 g of water and 160 g of 15% PPA and mix. Insert a copper tube through a small hole drilled in the lid of the blender. While mixing at the lowest speed, add 91 g of DETA into the tube with a 1 / 8 inch internal diameter, 2 g at a time. It takes about 7 minutes to add the DETA. The temperature of the solution rises to 155°F.

[0138] The solubility of the complex alkyl phosphate ester in polyphosphoric acid is unexpected, especially when heat of 50°C to 100°C is applied. This generalization is based on several esters that were dissolved in 115% PPA to form a CAPE-PPA solution to date. The CAPE-PPA was then reacted with EA to form a mixed component of EAPPA and ethylene amine complex alkyl phosphate ester.

[0139] Another class of compounds is formed by reacting a complex alkyl phosphate ester solution or a complex alkyl polyphosphate ester solution with ethylene amine and an alkali metal hydroxide, or reacting a complex alkyl sulfate ester solution with ethylene amine and an alkali metal hydroxide.

[0140] The above formulations for foaming are carried out at concentrations of 5% to 10% by weight relative to water. Formulations for making the foam will be made at high concentrations. Then, when used in actual fires, these concentrations are diluted by the addition of water.

[0141] Example 8 Synthesis of Aqueous Diethylenetriamine Ethoxylated (6) isotridecyl Phosphate:

[0142] Into a blender were mixed 20 g of ethoxylated (6) isotridecyl phosphate (Crodafos T6A), 7 g of glycol ether EB and 350 g of hot water (60°C). Next, 4 g of DETA was added while continuing to mix. The solution immediately foamed. 1200 ml of this foam was found to weigh about 236 g, with a 5.1 fold expansion. The pH was about 9.0. Ethoxylated (6) isotridecyl phosphate with 6 moles of EO is available from Croda Corporation as Crodafos T6A.

[0143] This experiment was repeated but with 3 g of DETA. 800 g of foam from the blender was found to weigh 182 g. The pH was about 8.3.

[0144] Example 9 DETA Ethoxylated Tridecyl Phosphate (CAPE):

[0145] The ingredients 120 g 8180, 7 g of ethylene glycol EB and 1100 g of hot water were mixed together in a blender. This mixture was then added to the blender with another 1000 g of hot water. Then 18 g of DETA was quickly added, mixed and allowed to continue for 5 minutes. The final solution pH was 8.3 and was called DETA ethoxylated tridecyl phosphate. This process was repeated 7 more times at which point it was added to a pressure tank. The tank was pressurized to 58 PSI and connected to a pressure washer Simpson 4000 PSI. The solution was sprayed through a Torq foam cannon which had 10 fine mist nozzles attached to it. The expansion rate was found to be 8.5, much higher than the previous example which used the thickening agent xanthan gum. This system successfully extinguished a 28 square foot tank fire with 5 gallons of regular gasoline in it. The foam that remained on top of the tank and covered the unburned gasoline showed anti-backdraft properties when subjected to a propane torch after 10 minutes.

[0146] Example 10 Formation of a Mixed Product of DETAPPA and DETA Ethoxylated Alcohol Phosphate Solution or Ethoxylated Alcohol Polyphosphate Solution:

[0147] A mixed composition of part ethylene amine polyphosphate and part ethylene amine complex alkyl phosphate can also be formed. The method of forming ethylene amine polyphosphate (EAPPA) includes the step of reacting ethylene amine (EA) and polyphosphoric acid (PPA) under substantially anhydrous conditions, at a reaction temperature, and at a reaction ratio of EA to PPA, such that the reaction of EA and PPA is substantially complete to form a solution (CA-PPA). The method will be followed except that the polyphosphoric acid and complex alkyl phosphate solution will be added to the reaction vessel in the given proportions. The temperature will typically be about 400°F to facilitate the extraction of the product. After the CA-PPA solution is formed, EA is added and the reaction is completed. The reaction product can then have the properties of a surfactant and a flame retardant. Fumed silica can also be added to the acid before the addition of EA to form a mixed doped product.

[0148] The flame retardant mixed composition of part ethylene amine polyphosphate and part ethylene amine complex alkyl phosphate solution is a flame retardant suitable for use in all thermoplastic and thermoset polymers, provided that the melting temperature of the polymer does not exceed the thermal stability of the mixed composition. Preferred polymers are olefins such as ethylene vinyl acetate (EVA), polyethylene, and polypropylene. Olefins are defined as macromolecular compounds having the general formula formed during the polymerization or copolymerization of unsaturated olefins (R, R' = H, CH3, C2H5, etc.). A typical composition for W&C applications consists of 0% to 1% fumed silica, 15% to 65% of the flame retardant mixed composition, and one or more EVA polymers, with 1-3% by weight of fumed silica in the flame retardant mixed composition. A skilled artisan of such compositions can add small amounts of ingredients for UV stability, color, thermal stability, etc.

[0149] Example 11 Anhydrous EA-Laurly Phosphate:

[0150] This anhydrous compound is specifically designed for use in flame retardant polymers. 60 g of LP is added to a 1.5 L pressure cooker. It is heated to about 150°C. At this point, about 11 g of DETA is added through the vent on the pressure cooker pressure release valve with a plastic pipette. The cooker is cooled to about 120°C and then opened. The product is mixed thoroughly with a spatula. The anhydrous DETA LP does not dissolve at room temperature. In contrast to PNS, which readily becomes sticky in humid air, a piece does not become sticky when left in humid air. It takes about 12 hours for it to become a little sticky. In humid air, a piece of PNS actually liquifies to about 70% concentration. The DETA LP does not liquify in humid air, which makes it a good candidate for addition to polymers.

[0151] Example 12: Anhydrous DETA (LP-PPA)

[0152] For polymer applications, a flame retardant with lower moisture sensitivity is needed. To this end, a sample of DETA was shown to react with a mixture of polyphosphoric acid and a complex alkyl phosphate solution. For example (CAPE-PPA), 48 g of 115% PPA and 48 g of lauryl phosphate were mixed together in a 1.5 L pressure cooker and heated to about 150°C to form a CAPE-PPA solution. The temperature must be such that the LP or any other complex alkyl phosphate melts and can be extracted. Then, 34 g of DETA was added using a pipette through a vented pressure reducing valve. Once there was very little smoke coming out of the vent, the composition was cooled to about 80°C and then opened. A spatula was used to mix the composition thoroughly. Some of the product was placed in water (10% by weight concentration) for a long time. The product DETA(PPA-LP) did not dissolve well, but a pH of 5.3 was obtained. A piece of 15 g of PNS and a similar size piece of the product were placed in a humid environment for 12 hours. The PNS became very sticky, while the product was not sticky at all, thus overcoming the limitation of PNS: moisture absorption. The sample that was subjected to a torch expanded well, but the char flaked off with a popping sound, probably because of the explosion of the lauryl content.

[0153] The same procedure was repeated with 54 g of 115% PPA (0.6 m), 25 g of LP (.09 m), and 34 g (0.33 m) of DETA, with 54 g of 115% PPA (0.6 m), 25 g of LP (.09 m), 4 g of glycol ether EB, and 34 g (0.33 m) of DETA, where m represents the number of moles, and at the temperature at which the LP and the final product melt. For both samples, a pH of 5.0 and 4.9, respectively, was found after placing a piece in stirred water for about 3 hours. Both were very low in moisture absorption compared to PNS. When a piece of DETA(PPA-LP) was subjected to a torch, the expanding char looked almost identical to PNS subjected to a torch. The glycol ether made no apparent difference. Since the amount of lauryl was reduced by half compared to the previous example of DETA(LP-PPA), there was also no sound of a rupture.

[0154] Example 13 CAPE: 60 g of PAE 147 (purchased from Lakeland Laboratory, Manchester, England) was added to a 1.5 L pressure cooker. PAE 147 has tetradecanol with 7 moles of EO and a monoester to diester ratio of 12:1. Then, 3.8 g of glycol ether EB was added to the PAE 147 and the mixture was heated. The pressure cooker was then sealed and 9 g of DETA was added through the pressure cooker's pressure regulator vent tube. The temperature was raised to 110°C at which time the lid was removed. The ingredients were thoroughly mixed using a spatula. A slowly flowing gel-like consistency was obtained. The gel solution appeared to be clear. Some of the gel was dissolved in water and the pH was 5.9. This composition can be used to form a concentrate which can then be diluted when used on a fire.

[0155] Example 14 CAPE: A second experiment was performed using 60 g of PAE 147, 10.5 g of DETA, 26 g of water and 3.8 g of glycol ether EB and the same procedure. The gel-like composition was much more flowable and the pH was 7.1. This composition can be used to form a concentrate which can then be diluted when used on a fire.

[0156] Again, the same procedure was used: 60 g of PAE 147, 3.8 g of glycol ether EB, 9.5 g of DETA. The composition was clear and dissolved in water to obtain a pH of 6.9. The composition can also form a concentrate and contain less EO.

[0157] Foams can be more effective if the EAPPA solution is added to the DETA ethoxylated tridecyl phosphate solution (CAPE). The EAPPA doped DETA ethoxylated tridecyl phosphate solution (CAPE-PPA) reacts more effectively with the flame but does not cause the foam to break. The above compounds can be made with other ethoxylated alcohols that form foams.

[0158] In general, the flame retardant polymer compositions formed with the EA-(complex alkyl phosphate-PPA solution) compositions are expected to have reduced water absorption due to the addition of the hydrophobic ester linkage compared to the flame retardant polymer compositions containing PNS which are extremely hygroscopic. For the flame retardant polymer compositions, it is preferred to add fumed silica to the CA-PPA solution prior to the addition of the DETA.

[0159] Fire extinguisher compositions for wild fires and building structure fires can use aqueous solutions of PNS up to about 50% concentration. This aqueous composition can be suitable for spillage of flammable liquid fires.

[0160] Military MILSPEC testing (MIL-F-24385F) limits foam concentration to 6%. Typically, FFF or AFFF foams are delivered as concentrates that are diluted with water at the fire scene to a concentration range of 3 to 6% by weight and applied. The examples of ethoxylated fatty alcohols described above have the ability to form concentrates. This concentrate can then be diluted with water at the time of manufacture and application of the foam when applied to a fire.

[0161] EA complex alkyl sulfates or EA complex alkyl sulfonates can be formed in a similar manner.

[0162] The expandability of the DETA LP foam compositions and the DETA ethoxylated tridecanol polyphosphates (n=2 and n=3) foam compositions were tested with a MILSPEC nozzle. Unfortunately, the foam expansion was only in the range of 2 to 4, much less than the values exhibited by the power washers and foam cannons in the examples to date. The primary reason is that the MILSPEC only operates at 100 PSI, and the foam solution is much slower than the pressure washers at 3000 to 4000 PSI. The MILSPEC nozzle can be converted to a foam cannon by replacing the dispersion cone with a 3 / 4 inch diameter wire mesh pill. This nozzle is then able to use a hollow cone nozzle array to form a thin mist with a large coverage area.

[0163] The next set of examples includes examples with expansion greater than 5 measured with an Amerex 250 foam extinguisher operating at 100 PSI and a MILSPEC nozzle operating at 100 PSI.

[0164] The compositions presented so far function in fire retardant polymers, wild fire extinguishment, and certain foams. The PNS introduced into the foam compositions has an impact on the foam expansion rate for the MILSPEC nozzle. Therefore, a new set of compositions is now introduced, which are called PNS-F. The PNS-F compositions have both fire retardant properties and blowing agent properties.

[0165] Another test method will now be added, along with new equipment connected to standard venturi-type foam nozzles (such as MILSPEC). The 28 square foot is too large to differentiate between compositions. Differentiation also requires multiple repeated tests, which is impractical with the 28 square foot test. The Department of Defense has another test called “Challenge 2021”. This test can be viewed on youtube.com as SERDP & ESTCP AFFF Challenge 2021 (https: / / www.challenge.gov / challenge / 2021-serdp-afff-challenge / ). In this test, foam is formed in a blender. The foam formed with the blender is applied by pouring it down a ramp (3.5 width, 2 inch sides) into a one square foot pan containing one inch of water and 500 ml of gasoline, which has been ignited and burning for 10 seconds. The amount of foam used to extinguish the fire is measured and recorded. One side of the ramp has a piece of cinder block, 16 inches high, 16 inches from the pan. This test will be used to compare various foam compositions. We will not report the extinguishment time because the fire will either quickly extinguish, or not all of it will be extinguished. In all of the FFF samples tested, the fire either quickly extinguished, or burned until smothered by a lid made of drywall. To make the test more realistic, a commercial Amerex 250 foam extinguisher or MILSPEC nozzle will be used to generate the foam, rather than using a blender. The foam is sprayed into a bucket and then poured on the ramp, the amount of foam used is weighed. It has been found that the Amerex 250 extinguisher and the MILSPEC nozzle have similar expansion rates.

[0166] It is also important to explore the best fatty acids (C8 to C14) rather than focusing only on ethoxylated tridecanol (primarily C13) as has been done to date. The degree of ethoxylation is also important, between 2 and 12. We have used a process that primarily forms monoesters.

[0167] The challenge test also allows us to optimize the ethoxylation. For tridecanol, the optimum number of moles of ethylene oxide (EO) is n = 6 to 12, with n = 9 being most preferred. Compositions with n = 0, 1, 2, or 3 have poor expansion with the Amerex 250 extinguisher. The poor expansion results in these compositions performing poorly in the challenge test.

[0168] The steric hindrance of EDA, DETA, TETA, TEPA, and piperazine can be significantly different. The ionic strength can be EA dependent. Properties such as emulsification, wetting, and surface tension can affect the diffusion coefficient. The amount of foam required to extinguish a gasoline fire for a 1 square foot gasoline fire is very sensitive to the degree of ethoxylation. As the study extends beyond DETA to other ethylene amines, other factors are expected to be important.

[0169] It is important to observe the formation of SLES with EA instead of sodium. Currently, SLES is made with ethoxylation n = 1 and 2 only. This SLES ingredient is not optimized to pass MILSPEC. It is envisioned to make EA ethoxylated fatty alcohol sulfates with ethoxylation n up to 12. Thus, the general compound is ethylene amine ethoxylated fatty alcohol sulfates where n = 1 to 12 and the fatty alcohol is C8 to C14.

[0170] Control: As a control, the first test was National Foam General Green 3%. A 2100 g solution was formed from the National Foam product at 3% concentration and added to an Amerex fire extinguisher pressurized to 100 psi. The foam was sprayed into the bucket and then the pan fire was ignited. After 10 seconds, the foam was poured down the slope. Surprisingly, 330 g of foam was required to extinguish the pan fire containing 500 ml of gasoline and 1 inch of water. The expansion ratio was only 3.5, which was also unexpectedly low. For the National Foam concentrate, the foam produced with a pressure washer and a Torq foam cannon had a higher expansion value of at least 5. So far, FFF compositions including the compositions of the present invention form higher expansion ratios with pressure washer / foam cannon devices than with commercial Amerex 250 foam extinguishers. By selecting the appropriate ethoxylation n and fatty alcohol, the difference in expandability can be greatly reduced.

[0171] A new FF foam composition that uses a surfactant formed by reacting EA with an ethoxylated tridecanol polyphosphate solution (n = 9-12) (CA-PPA) with a high expansion ratio of 6-9 with an Amerex 250 foam extinguisher is now provided.

[0172] Example 15 Formation of Ethoxylated Tridecanol Polyphosphate Solution (CA-PPA): To a one quart stainless steel pressure cooker was added 51 g of 115% PPA and 225 g of ethoxylated tridecanol. Samples of ethoxylated alcohols with n = 3, 6, 9, 12, 18 were produced. Other ratios of acid to alcohol were tried (51 g, 265 g and 65 g, 225 g) but the best results were with 51 g and 225 g. The cooker was sealed and heated to 400°F in a closed propane oven for about 5 minutes. The cooker was opened and then mixed for about 5 minutes while still hot. After about 3-5 minutes, the PPA and alcohol were mixed together with a spatula to form a clear solution of anhydrous ethoxylated tridecanol polyphosphate solution. The clear solution was stable and remained stable regardless of temperature. For ethoxylations of n = 1 or n = 2, the reaction was more difficult and took longer. There was no way to know exactly what was formed other than by its performance and repeatability. Thus, an ethoxylated tridecanol polyphosphate solution was formed by this process which was believed to be primarily a monoester polyphosphate. Due to the large size of the ester molecule, steric hindrance can affect the composition.

[0173] Example 16 Formation of Diethylenetriamine Ethoxylated Tridecanol Polyphosphate (DLEPP): A total of 2000 g of water was collected in all samples. This sample size was large enough to run four Challenge 2021 tests at different amounts of foam. In the first step, 66.7 g of ethoxylated tridecanol polyphosphate solution was mixed with 15 g of diol ether EB and then added to 1500 g of water in a blender. DETA was added to bring the pH between 7.2 and 7.5 depending on the degree of ethoxylation n, which was about 11 g to 12 g of DETA. 1 g to 5 g of xanthan gum was dissolved in 350 g of water in a blender to form an opaque solution. The xanthan gum solution was mixed to form the FFF. This solution was added to an Amerex 250 foam extinguisher and pressurized to 100 psi. In four tests, the challenge was passed at 184 g and 208 g, but failed at 160 g and 170 g. 170 g came close to extinguishing but did not due to marginal burning. The tests were repeated and these results were representative. The test at n = 3 did not perform well because of solubility issues, forming a sol or hazy solution. The test at n = 9 was almost as good as the test at n = 12. The test at n = 6 was acceptable because it passed the challenge at 200-210 g.

[0174] The preferred ingredient ratios for an Amerex 250 extinguisher are more restrictive than for a pressure washer. Pressure washers with foam cannons can produce good foam over a wider range of ingredients than traditional extinguishers. Then more fire retardant compositions are achieved with the pressure washer device.

[0175] Alkyl polyglycosides are obtained from renewable raw materials by reacting a mixture of one or more alcohols with glucose or glucose polymers. These surfactants are typically glucose derivatives and fatty alcohols. The raw materials are typically starch and fats and the end product is typically a complex mixture of compounds with different sugars comprising the hydrophilic end and variable length alkyl groups comprising the hydrophobic end. When derived from glucose, they are called alkyl polyglycosides. Alkyl glycosides are produced by combining a sugar (e.g. glucose) with a fatty alcohol in the presence of an acid catalyst at elevated temperatures: lauryl glycoside (glucose + lauryl (C12-C14), alcohol), decyl glycoside (60% C8-C10, 40% C12-C14), coco glycoside (40% C8-C10, 60% C12-C14). Ingredients containing decyl glycoside foam quickly, but the foam also disappears quickly compared to other ingredients. Low viscosity exhibits excellent fluid flow properties. Decyl glycoside was first used in soaps and body cleansers because it has a strong foaming power. Foaming surfactants are detergents whose HLB (hydrophilic-lipophilic balance) values are different from emulsifying surfactants. The HLB of foaming surfactants is typically greater than 18, preferably greater than 20. Liquid surfactants are diluted with water, providing an active content of 50% to 70%. The unbleached grade is indicated by the index "DK" and is a brownish liquid, while the bleached grade is a colorless to pale yellow liquid. In contrast to fatty alcohol ethoxylates, they have much stronger foaming properties. In addition, they have excellent solubilizing and film-forming properties. Alkyl polyglycosides can be applied as foaming agents in fire-fighting equipment.

[0176] BASF produces Glucopon® (alkyl polyglycoside) is a nonionic surfactant that is considered a replacement for sulfated surfactants. Alkyl polyglycosides are made from saturated natural alcohols and glucose, where the alkyl group has about 8 to about 14 carbon atoms. Glucopon 225 dk produced by BASF has C8-C10 alcohols, moderate foaming properties, and base stability up to a pH of 13.

[0177] Example 16 DLEPP-Glucopon 225 DK Foam (CA-PPA):

[0178] Glucopon 225DK can be added directly to any FFF composition. Glucopon 225DK can be added directly to any CA-PPA, CA-PA, or CAPE-PPA composition. For example, LEPP12 was formed by reacting 51 g of 15% PPA and 225 g of Makon DT12 to form a clear solution. Next, 66 g of LEPP12 was mixed with 15 g of glycol ether EB, then 50% water was added. 10 g of Glucopon 225DK was added. Then, 1700 g of water and 13 g of DETA were added to the solution to give a pH of 7.4. The last step was to add 0.75 g of xanthan gum dissolved in 250 g of water to form DLEPP. The DLEPP was added to an Amerex 250 fire extinguisher and pressurized to 100 psi. The foam produced by the Amerex 250 foam fire extinguisher passed the challenge test at 240 g, 218 g, and 187 g.

[0179] Example 17 PPA-Glucosinolate (CA-PPA):

[0180] Due to the color of Glucopon 225DK, 51 g of PPA and 225 g of Glucopon 225 were reacted at 140 F to form a tan solution. 2000 g of water was weighed out. 65 g of the tan solution was mixed with 15 g of glycol ether EB. About 100 g of water was added, then another 1000 g of water was added. Then DETA was added until the pH reached 7-8.5, which was about 11 g. The CA-PPA solution was added to an Amerex 250 fire extinguisher, which produced a foam with an expansion greater than 5 that performed well in the Challenge 2021 test.

[0181] This example (CA-PPA) shows that a FF foam composition with very good expansion can be formed by using a complex alkyl polyphosphate solution without the need for a glycol ether solvent. First, 100 g of PPA and 175 g of Makon DA9 were reacted together. The actual composition can vary depending on the reaction being run at different temperatures or for different lengths of time. Those familiar with such compounds will resolve this dependency. Then, 131 g of this solution was mixed with 5 g of xanthan gum dissolved in 250 g of water, which had a pH of 1.75. To this solution, 40 g of DETA was added, which had a pH of 7. The expansion of the foam produced with a MILSPEC nozzle was 7.6. This foam extinguished fires from 200 g to 235 g in the challenge test. We ran this example again, but also added 30 g of Glucopon 225DK. The expansion increased to 8.1. The results of the challenge test were similar. Thus, a good expansion was obtained without the need for a glycol ether. This FF foam is more environmentally friendly since no glycol ether is used.

[0182] Example 18 (CA-PPA) 100 g PPA was reacted with 175 g Makon DA9 at 400°F to form a clear solution. Then, 80 g DETA was added slowly, but some escaped. This composition did not dissolve easily in water and required a lot of mixing. 22 g of this compound was dissolved in hot water with a pH of only 5.8. DETA was added to make the pH 7. This solution was added to 5 g xanthan gum dissolved in 11 g glycol ether and 1000 g water. Separately, 50 g Solberg RF3 concentrate was dissolved in 1000 g water. These solutions were mixed together. The solution was added to a 100 PSI pressure tank. The MILSPEC nozzle produced a foam expansion of 4.6. 216 g of the foam was added to a 1 square foot pan of gasoline and the fire was extinguished. This is not preferred because dissolving DETA ethoxylated fatty alcohol PPA in water is difficult. For foam and wild fire applications, it is easier and preferred to dissolve the solution in a small amount of water and then add DETA or some other ethylene amine.

[0183] To date, the 1 square foot test was performed outdoors and it was found that the wind caused the results to vary. For the following tests, three 30 inch by 5 foot panels were constructed of sheet metal and 2 by 4 inch wood braces. The panels were secured together by door hinges. The panels were positioned to almost enclose a 1 by 1 foot pan in a triangle. The space between the panels was about 12 inches so that a person could reach in and pour the MILSPEC nozzle produced foam into the ramp. The metal panels kept the heat and flame inside and the wind and air currents outside so the results had acceptable reproducibility. It was not necessary to perform a control burn every day with Solberg RF3.

[0184] The following examples represent the best performing CA-PPA samples as well as a control Solberg RF3 based on the results of the challenge test. All of these were performed with the same procedure:

[0185] 1) For the 1 square foot challenge test, all compositions were formed using the same process. The composition was formed by the following reaction. First, 100 g of PPA was reacted with 175 g of Makon 6 at a temperature of 400 °F to form a clear CA-PPA solution that was brown in color. Next, 50 g of this solution was dissolved in 200 g of water. This solution was then reacted with 15.5 g of DETA. Then 12 g of Silwet L-77 was added and mixed. Separately, 2.2 g of xanthan gum was mixed with 11 g of glycol ether EB and then added to 2000 g of water. The two solutions were mixed together. The solution was added to a tank that was pressurized to 100 PSI and connected to a Milspec nozzle. Several challenge tests were performed. The expansion rate of this foam was 8.4. In the 1 square foot test, 500 ml of E0 gasoline was successfully extinguished with 150 g and 157 g of foam. This sample was also tested at 28 square feet at the Naval Research Laboratory, which is the official testing site for MILSPEC testing. The extinguishment time was 85 seconds. The flash back time was 3 minutes. It was observed that the foam blanket deteriorated during the test. The flash back time was also shortened due to the flame penetrating through the foam blanket. It will be shown later that more xanthan gum needs to be added to increase the flash back time.

[0186] 2) For the next examples, the same process as the 1 square foot test will be used to give the composition and results with 500 ml of E0 gas and a MILSPEC nozzle to form the foam. 100 g of PPA was mixed with 175 g of Makon DA6 at 400 °F to form a solution. 50 g of this solution was mixed with 2200 g of water, 5 g of xanthan gum, 11 g of glycol ether EB, 12 g of Silwet L-77, 14.5 g of DETA to give a solution with a pH of 7.8. The expansion rate was 8.0. The 1 square foot test was passed with 186 g and was substantially passed with 160 g.

[0187] 3) The next example mixed 100 g of PPA with 175 g of Makon UD8 at 400 °F. 50 g of this solution was mixed with 2200 g of water, 5 g of xanthan gum, 11 g of glycol ether EB, 12 g of Silwet L-77, and 16 g of DETA to give a solution with a pH of 6.8. The expansion rate was 6.3. The 1 square foot test was passed with 182 g, 174 g, and 176 g.

[0188] 4) The next example mixed 75 g PPA with 200 g Makon DA6 at 400 °F. 50 g of this solution was mixed with 2200 g water, 5 g xanthan gum, 11 g glycol ether EB, 12 g Silwet L-77, and 13.3 g DETA to give a solution with a pH of 6.9. The swell rate was 9.0. The 1 square foot test passed at 170 g, 172 g, and 207 g.

[0189] 5) The next example mixed 75 g PPA with 200 g Makon DA6 at 400 °F. 50 g of this solution was mixed with 2200 g water, 5 g xanthan gum, 11 g glycol ether EB, 12 g Glucopon 225DK, and 13.2 g DETA to give a solution with a pH of 7.1. The swell rate was 10.4. The 1 square foot test passed at 151 g, 159 g, but failed at 132 g.

[0190] 6) The next example mixed 100 g PPA with 175 g Makon DA6 at 400 °F. 50 g of this solution was mixed with 2200 g water, 5 g xanthan gum, 11 g glycol ether EB, 10 g Glucopon 225DK, and 14.2 g DETA to give a solution with a pH of 7. The swell rate was 8.8. The 1 square foot test passed at 166 g, 171 g, but failed at 144 g.

[0191] 7) The next example mixed 100 g PPA with 175 g Makon DA9 at 400 °F. 50 g of this solution was mixed with 2200 g water, 5 g xanthan gum, 11 g glycol ether EB, 10 g Glucopon 225DK, and 14.9 g DETA to give a solution with a pH of 7.1. The swell rate was 9.3. The 1 square foot test passed at 167 g, 188 g, but failed at 161 g. Using 85 (MW (molecular weight) of PPA) and 422 (MW of Makon DA 6) (158 mw alcohol + 6 mw EO), 50 g of CA-PPA solution is equivalent to 0.21 m PPA and 0.08 m Makon DA 6. The mw of DETA is 103, using 0.15 m DETA gives a pH of 7.1. Thus, the ratio of these molecular weights is unexpected and unexplainable. Unexpectedly, the ratio of PPA to EA is very different from the ratio used to form EAPPA in PCT / 19 / 034077 and PCT / 20 / 52061. The ratio of CA to PPA is unexpected. The ratio of the molecular weights of the examples throughout the specification is unexpected.

[0192] 8) The next example mixed 100 g PPA with 175 g Makon DA9 at 400°F. 50 g of this solution was mixed with 2200 g water, 10 g Crodafos T6A, 5 g xanthan gum, 5.1 Silwet L-77, 11 g glycol ether EB, and 15 g DETA to give a solution with a pH of 6.8. The swell rate was 7.7. The 1 square foot test was passed at 169 g, 180 g, and 246 g. This example shows that adding Crodafos T6A phosphate ester as an additive is effective in a 1 square foot fire.

[0193] 9) For the control, 68 g Solberg RF3 was mixed with 2200 g water. The 1 square foot test was run the same as the others. The swell rate was 6.1. The 1 square foot test was passed at 210 g, 201 g, but failed at 193 g.

[0194] 10) The next example mixed 100 g PPA with 175 g Makon DA9 at 400°F to form a solution. 22 g of this solution was mixed with 2200 g water, 38 g Solberg RF3, 4 g xanthan gum, 11 g glycol ether EB, and 7.4 g DETA to give a solution with a pH of 7.4 and a swell rate of 7.1. The 1 square foot (sqft) test was passed at 233, but failed at 197 g. By adding the DETA complex alkyl polyphosphate solution, the Solberg RF3 had a better swell rate, but the 1 square foot performance was essentially the same.

[0195] 11) The next example mixed 22 g Crodafos T6A with 2200 g water, 38 g Solberg RF3, 4 g xanthan gum, 11 g glycol ether EB, and 3.8 g DETA to give a solution with a pH of 7.4 and a swell rate of 2.44. It appears that the phosphate ester Crodafos T6A resulted in an unacceptable foam swell rate.

[0196] 12) The next example mixed 87 g PPA with 188 g Makon UD5 at 400°F to form a solution with a pH of 1.5 when mixed with water. 38.2 g of this solution was mixed with 7.6 g Glucopon 225DK, 2200 g water, 1.7 g xanthan gum, 8.4 g glycol ether EB, and 11 g DETA to give a solution with a pH of 7.1 and a swell rate of 11.1. The 1 square foot test was passed at 177 g, 175 g, and 135 g. This example performed the best at 1 square foot, with a concentration of only 3%. It appears that reducing the amount of thickening agent improved the performance.

[0197] The sample was tested at 28 square feet at NRL and passed the MILSPEC test. The extinguishment time was 83 seconds and the reignition time was 2 minutes and 45 seconds. The foam blanket was burned through as the test progressed.

[0198] 13) The next example mixed 87 g PPA with 188 g Makon TD3 at 400°F to form a solution with a pH of 1.6 in a 10% water solution. 38.2 g of this solution was mixed with 7.6 g Glucopon 225DK, 2200 g water, 1.7 g xanthan gum, 8.4 g glycol ether EB, and 10 g DETA to give a solution with a pH of 7.1 and an expansion of 6.6. 233 g passed the 1 square foot test and 184 g failed. This example showed poor performance at 1 square foot and 3% concentration. Of particular interest is that the foam solution was hazy, which indicates that all of the ingredients did not fully dissolve. If the concentrate is allowed to sit for months, the particulates would be a major problem. Therefore, Makon TD 3 with 3 EO does not have good solubility like Makon UD5 and would not be considered a candidate for FFF. Makon TD-3 can be a candidate for polymer and wildland applications.

[0199] The first 8 compositions along with 12) are considered the best candidates to pass the 28 square foot test. The number of tests performed at 28 square feet is limited, so it is unlikely that the Makon DA9 compositions will be tested. These compositions have a total concentration of 3.9% or 3% relative to the total weight. The variables that still need to be tested are pH, glycol ether, other ethoxylated fatty alcohols, silicone surfactants, and alkyl polyglycosides. However, this will be determined after the 28 square foot test burns with 10 gallons of E0 gasoline.

[0200] It is preferred to use a single strand of foam with a MILSPEC sample nozzle to extinguish a tank fire. It is more preferred to use a pressure washer that applies a large area of fine mist of foam to the fire, with the foam mist particles collecting on the surface and forming a barrier on the surface. The mist is composed of droplets with a volume median diameter (VMD) of less than 1500 microns, or preferably less than 600 microns, or more preferably less than 400 microns, or even more preferably less than 200 microns, or most preferably less than 75 microns. Unfortunately, testing agencies such as the US Department of Defense (DOD) and only use a single strand of foam, which is the procedure that applies to these FFFs.

[0201] Another test is now introduced to test for burn through of the foam blanket and flash back or reignition. This test will be referred to as the tub test. AFFF foams are known to have much better burn through and flash back performance than FFF. A standard metal tub is obtained from a hardware store with a base of 3.14 square feet (24 inches in diameter), 13 inches sides, tapering up. The bottom diameter is 2 feet and the top diameter is 2 feet 6 inches. Two gallons of water and 1100 g (1375 ml) of E10 gasoline are always added to the tub before the test begins. As a reference, the MILSPEC flash back test contains 3780 ml of gasoline for a 28 square foot fire. The FFF solution is then made into foam by adding the FFF solution to a pressure tank, pressurized to 100 PSI, and sprayed into foam with a MILSPEC nozzle. The foam expansion rate is measured. 600 g of foam is collected in a bucket and poured into the tub containing the water and gas. A heavy metal pan containing 450 g (1375 ml) of E10 gasoline is placed in the center of the tub and lit. This is all done within 30 seconds to prevent foam degradation. The pan is lit. The heat from the gasoline burning causes the foam to degrade and the vapors to permeate from under the foam blanket and from the gasoline on top of the water surface. Initially, the flame height is only about 12-18" high as only the gas in the pan is feeding the flame. The flame height can be seen to grow to 5 feet high which is fed by the vapors permeating through the foam blanket. After about 2 minutes, the foam blanket starts to burn and the test is stopped by placing a lid on the tub. One can observe that as the fire develops, the foam blanket thins and then the blanket is unable to contain the vapor emissions.

[0202] A number of FFF foam solutions (CA-PPA and CA-SA) have been prepared and tested with the tub test. Each FFF composition was prepared following the same procedure. The FFF composition was formed by mixing 96% sulfuric acid or 115% PPA together with an ethoxylated alcohol, Makon DA4 or Makon UD5. The SA was done at room temperature while the PPA was done at 400°F in a propane oven. Then, 2200 g of water was mixed with 50 g of the sulfuric acid-ethoxylated alcohol solution or 50 g of the PPA-ethoxylated alcohol solution. DETA was added to obtain a pH of 7 to 8. Separately, 5 g of xanthan gum or diutan was mixed with 1100 g of water. The two solutions were mixed together to form the FFF without glycol ether. The solution was placed in a pressure tank and pressurized to 100 PSI. The MILSPEC nozzle was used to create the foam and 600 g was collected in a bucket. The foam was poured on the tub described earlier which already contained 2 gallons of water and 1100 g of E10 gasoline. A metal pan containing 450 g of E10 gasoline was placed in the center and lit. The time until about ½ of the tub was covered by the flame was recorded.

[0203] The first example was a control made with 600 g of 3% Solberg RF3 solution dispersed in a 2 gallon bucket of water. The test was run by placing a pan containing 450 g of gasoline and it took 115 seconds to extinguish the fire. The expansion rate was 8.47.

[0204] The next example was made by reacting 87 g of PPA with 188 g of Makon UD5. The FFF foam was made from 50 g of this solution, 2200 g of water and DETA to give a pH of 7. The flame had to be extinguished in 23 seconds and the expansion rate was 10.03. The results were very poor due to the lack of xanthan gum or diutan. The next example contained the same ingredients but with 5 g of xanthan gum added. The fire was extinguished in 143 seconds and the expansion rate was 10.8. The exact time to burn 1 / 2 of the area was somewhat subjective and was in the 15 second range. All bucket test results should include a 15 second line of expected error. These examples also show that the organic solvent can be eliminated to make the formulation more environmentally friendly.

[0205] The next bucket test example was identical except that it contained sulfuric acid (SA) and used Makon DA4. The ratio of SA to Makon DA4 was chosen to be 72 g to (to) 203 g, 87 g to 188 g, 100 g to 175 g and 125 g to 150 g. These samples turned purple at room temperature, appeared to be fully reacted and the temperature from the exothermic reaction reached 185 °F. The composition was then made up of 2200 g of water, 50 g of SA and Makon DA4 in one of the four ratios, 5 g of diutan and then neutralized with DETA. Good performance was obtained without the need for glycol ether. For 72 g of SA to 203 g of Makon DA4, the extinguishment time in the bucket test was 128 seconds and the expansion rate was 15.2. For 87 g of SA to 188 g of Makon DA4, the extinguishment time was 210 seconds and the expansion rate was 9.76. For 100 g of SA to 175 g of Makon DA4, the extinguishment time was 135 seconds and the expansion rate was 10.3. For 125 g of SA to 150 g of Makon DA4, the extinguishment time was 120 seconds and the expansion rate was 9.6. The best results were 87, 188 which was unexpected. Similar results were found by replacing Makon DA4 with Makon UD5.

[0206] The results show that the extinguishing time for RF3 control was 115 seconds, which is comparable or shorter than many of our examples using SA. The expansion rates for RF3 tended to be less than our examples. Surprisingly, the SA / ethoxylated alcohol / DIUTAN / DETA formed a FFF that was effective over a wide range of compositions. These results were unexpected. We are not aware of ethoxylated sulfates being made over a wide range of compositions. SLES is made from ethoxylated lauryl alcohol with one or two EO. In addition to the fact that we observed a foam with fire extinguishing capabilities over a wide range of compositions, the bonding of our compositions is inexplicable.

[0207] In the following examples, the ratio of PPA to Makon DA4 was selected to be 72g to 203g, 87g to 188g, 100g to 175g and 125g to 150g. The composition was then made up of 2200g water, 50g PPA and one of the four ratios of Makon DA4, 5g DIUTAN and then neutralized with DETA. No glycol ether was used. These samples turned a light tan color at room temperature and appeared not to be fully reacted. We heated these samples to 400°F to ensure the reaction was complete. For 72g PPA to 203g Makon DA4, the bucket test extinguishing time was 135 seconds and the expansion rate was 7.10. For 87g PPA to 188g Makon DA4, the extinguishing time was 195 seconds and the expansion rate was 10.16. For 100g PPA to 175g Makon DA4, the extinguishing time was 120 seconds and the expansion rate was 8.4. For 125g PPA to 150g Makon DA4, the bucket test extinguishing time was 104 seconds and the expansion rate was 11.54.

[0208] The bucket test shows that FFF foams from sulfuric acid, DETA, ethoxylated alcohol and thickener provide a preferred fire extinguishing foam composition. Almost equally good performance can be obtained with PPA in place of SA.

[0209] 1 square foot test is the fastest test and shows possible compositions and their expansion rates. This test does not involve whether the foam has good backflash. The bucket test differentiates backflash behavior and indicates that thickening agents are necessary to get good backflash behavior. These tests show that adding PNS to FFF is not as effective as adding PNS-F to FFF in terms of backflash resistance. These tests further show that foams made with PNS and SLES are not as effective as PNS-F in terms of backflash resistance. The expansion rate of foams made with PNS and SLES is lower than the expansion rate of foams made with PNS-F using the MILSPEC nozzle. The expansion rate of foams made with PNS added to FFF is lower than the expansion rate of foams made with PNS-F using the MILSPEC nozzle. Our data consistently show that foams made with PNS-F have superior expansion rates to Solberg RF3. PNS-F made with PPA and EA self-expand. PNS-F made with SA and EA do not self-expand as much as PPA-EA derived PNS-F. The combination of SA for viscosity and PPA for self-expansion can be more preferred.

[0210] It appears that diutan gum is more effective than xanthan gum, possibly because diutan has a higher molecular weight (mw) than xanthan gum. A literature search on Google shows that diutan has a molecular weight (MW) of 1,000,000 g / mol, while xanthan gum has a molecular weight of only 933 g / mol, which can be the reason for diutan’s success.

[0211] Both diutan and xanthan gum are used in drilling fluids. A Google search shows as follows. Xanthan gum is commonly used in drilling fluids to provide viscosity, solids suspension, and fluid loss control. However, xanthan gum is sensitive to high temperatures and does not tolerate field contaminants. Diutan gum provides the same functionality but overcomes the deficiencies of xanthan gum. Diutan’s higher temperature resistance is very important for backflash and burn-through resistance in cases where the foam blanket needs to resist very high temperatures.

[0212] CP Kelco shared the following non-public information. CP Kelco supplies xanthan gum and diutan. CP Kelco states that their xanthan gum has a MW of approximately 2 million Daltons, while diutan gum has a MW of approximately 2.85-5.2 million Daltons. CP Kelco points out that diutan gum is in fact much longer molecule than xanthan gum because 2 / 3 of its molecular weight is in the backbone of the molecule, which makes it longer than xanthan gum, which has 3 / 5 of its molecular weight in side chains, thus xanthan gum is larger and shorter than diutan gum. CP Kelco’s analysis is based on AFM (Atomic Force Microscopy), which indicates that diutan molecules are about 4-5 times longer than xanthan molecules. CP Kelco believes that at the same concentration, a higher molecular weight bio-gum should provide better foam stability than a lower molecular weight bio-gum.

[0213] Makon DA4 is a c10 isodecyl alcohol with a molecular weight of 158. The addition of 4 EO makes the molecular weight of Makon DA4 approximately 324. Thus, the reaction for 87SA, 188 Makon DA4, and DETA involves 0.16 moles of SA, 0.11 moles of Makon DA4, and 0.13 moles of DETA (same as the titer for SA, which is 2). There is no way to justify these molar ratios. It appears that a substantial reaction of SA and DETA has occurred, resulting in a flame retardant. The formulation contains 0.18 moles of PPA, 0.11 moles of Makon DA4, 0.14 moles of DETA, and a small amount of diutan. These ratios are similar to the ratios of SA, Makon DA4, DETA, and diutan. The ratios of the reactants cannot be justified based on the formation of traditional ester bonds, as the formation of traditional ester bonds is believed to occur in compounds such as SLES. Furthermore, similar performance is observed for SA and PPA, where the ratio of acid to ethoxylated alcohol varies greatly. We have been able to avoid the use of glycol ethers to reduce the amount of flammable ingredients. Organic solvents are not environmentally friendly. Despite the heat and flame, very high molecular weight diutan gum holds the ingredients together. The foam solution has the consistency of a soap concentrate due to the thickening agent.

[0214] 1 square foot tests and bucket tests are helpful, but do not address the question of whether the foam will spread rapidly to form a foam blanket in a large box fire. It is necessary to do several 28 square foot tests to select the best performing composition. We will find that spraying these foam compositions on large gas fires, even if the spread is slow, will extinguish the fire.

[0215] In the literature from Spraying Systems and Teejet, it is stated that in any purely hydraulic nozzle, the hollow cone produces the smallest average droplet size. Of any hollow cone, the axial hollow cone produces the smallest droplet size. Here, only the hollow cone nozzles that spray a fine mist are used. The Teejet literature states that the production of a fine mist spray means that the droplets can be absorbed more quickly, cool more quickly, and the wetting effect is best. These three properties are ideal for the fire fighting foam application described herein.

[0216] Hollow cone nozzles can be simple or complex. Lechler offers a hollow cone nozzle that contains a spiral groove that spins the liquid before it exits. This is very expensive. Spraying Systems offers an expensive hollow cone axial flow nozzle where the liquid passes through a slot as it spins in a circular path. Teejet makes a simpler, less expensive hollow cone nozzle (Conejet Visio Flow hollow cone tip) that consists of a plug that is easily removed that prevents the liquid from passing directly through the nozzle. These nozzles with simple designs are very inexpensive and light weight compared to the nozzles that spin the liquid. The Teejet nozzles are best suited for our fire fighting foam application.

[0217] The best samples from the bucket test will now be repeated for the 28 square foot test with 4 gallons of E10 gasoline. As outlined in the protocol, the test will first be performed with the MILSPEC nozzles that spray a single strand of foam. The CA-PPA foam (150g PPA, 150g Makon UD5, 13200g H2O, 33g xanthan gum, 48g glycol ether) and the CA-SA (150g SA, 150g Makon UD5, 13200g H2O, 33g xanthan gum, 48g glycol ether) foams perform similarly with the MILSPEC nozzles that spray a single strand. When sprayed as a single strand, the extinguishment times vary from 60 seconds to 80 seconds. The foam does not spread quickly and takes a long time to form a blanket of foam over the gasoline surface. It seems unlikely that the gasoline fire can be extinguished with a single strand in 30 seconds (which is the goal of the MILSPEC test). The foam itself looks stable and forms a good blanket. It is just lacking the rapid spread of an AFFF foam.

[0218] Now we will attempt to achieve the 30 second goal by using boom sprayers of hollow cone nozzles arranged to provide a large coverage area to cover the surface of the tank in a few seconds. The boom will contain 7-12 hollow cone nozzles. The boom will be connected to a Torq foam cannon which is connected to a telescoping pole which is connected to a 50 foot 3 / 8" hose powered by a pressure washer. A feed tank containing a foam solution pressurized to 50 PSI is connected to the intake line of the pressure washer. The foam solution from the feed tank is propelled through the 50 foot hose, through the telescoping pole, through the foam cannon, then through the boom, and out of the hollow cone nozzles in a fine mist. The pressure at the individual nozzles is measured to be approximately 65 PSI.

[0219] A 3 / 4 inch male copper fitting is welded to the Torq foam cannon. The boom is rectangular in shape with one side being 11" and the other side being 7". Attached to each corner is a triangle (base 5", height 5") of three hollow cone nozzles. The boom is connected to a telescoping pole so that the fire can be extinguished at a distance of at least 10 feet. The fine mist is formed by 12 Teejet Conejet TX-12 nozzles. The solution is made from 13,200 g of water, 150 g of SA at 98% concentration reacted with 150 g of Makon UD5, 33 g of xanthan gum, 48 g of glycol ether, and about 145 g of DETA to obtain a pH of close to 7.0. Thus, the sample contains (145+150) FR and 150 g of surfactant. About 14 L of the solution is placed in a tank held at 50 PSI pressure and connected to a pressure washer. Four gallons of E10 gasoline is placed in a 28 square foot circular tank with 1 inch of water and then ignited. The above described apparatus forms a spray that looks like and behaves like a mist. The pole with the foam cannon / boom is moved in a circular motion around the edge of the tank. After 4 trials, the fire is extinguished in 15 to 22 seconds followed by the formation of a continuous foam blanket. The mist sprayed as a large coverage area accumulates on the surface as a partial foam barrier. We believe that the high surface area of the mist both cools the flame and reacts with the free radicals in the flame. It is important to spray the sides of the tank in the event of a reflash due to the hot metal tank sides. The 15 second time is too short to form a continuous foam blanket with a foam that has a low diffusivity. After the fire is out, a film is formed on the surface and a foam is formed over most of the tank. Similar results are found for a mixture of 6 Teejet Conejet TX-12 and 6 TX-10 nozzles or 12 Teejet Conejet TX-18 nozzles. Some char is observed on the surface and a continuous film / coating is observed after the gasoline fire is extinguished. The pressure is measured to be 65 PSI at one nozzle. The PSI is reduced by the flow wire mesh particle. The pressure is distributed over the 12 nozzles and is only 65 PSI when spraying water.

[0220] Replacement of the flat nozzle resulted in an extinguishment time greater than 30 seconds. The flat nozzle hits the gasoline surface with a much higher impact force, creating large waves, and makes extinguishment more difficult due to reflash.

[0221] A solution made from 13,200 g of water, 150 g of SA at 98% concentration reacted with 150 g of Makon UD5, 33 g of xanthan gum, 48 g of glycol ether, 145 g of DETA (pH equal to 7.0) extinguished a 4 gallon E10 gasoline fire in 15.8 seconds. The fire was initially about 40 feet high and nothing was visible on the other side of the fire. At 7.5 seconds, the fire was about 5 feet high and occupied about ½ of the tank and the other side of the fire was visible. At 11 seconds, about 90% of the fire was extinguished. At 14 seconds, there was still a small amount of flame on one side edge. The foam formed a thin blanket over about ½ of the 28 square foot tank. The conclusion is that the thin mist form of foam from the atomized hollow cone nozzle has cooled the fire so there is no danger of reflash. The fire was extinguished so rapidly due in part to the reaction with free radicals and cooling. Cooling the flame also reduces free radicals, thus rapidly reducing the flame. These tests are too difficult and costly to carefully study different parameters. We must rely on simple tests such as the 1 square foot test and the bucket test to select the best composition.

[0222] Similar results were found using a solution made from 13,200 g of water, 150 g of 115% PPA reacted with 150 g of Makon UD5, 33 g of xanthan gum, 48 g of glycol ether, and about 140 g to 150 g of DETA (pH brought close to 7.0). The PPA version had more char on the post-fire surface compared to the SA version. The SA reaction with Makon UD5 was done at room temperature and formed a hot purple solution with foam bubbles on the surface and some odor. The PPA reaction with Makon UD5 was done at 400°F. The PPA-Makon UD5 product solution cooled to a very thick state and was difficult to dissolve in water. The SA-Makon UD5 was easy to pour at room temperature and easy to dissolve in water, which is a big advantage in forming concentrates. Low viscosity is a general property of SA reactions with complex alkyl compounds.

[0223] Similar results were found using 225 g of UD5 reacted with 75 g of SA or 75 g of PPA and then reacted with about 70 g of DETA. Similar results were found using 200 g of UD5 reacted with 100 g of SA or 100 g of PPA and then reacted with about 90 g to 95 g of DETA. The 1 square foot and bucket tests indicate that as the ratio of acid to UD5 increases, the thermal stability is better, which is important for real large fires.

[0224] The fire was extinguished even though the foam blanket was discontinuous. If we sprayed the metal outer wall of the tank in a circular pattern, the fire was quickly extinguished. The spray rate was measured to be 2.5 GPM. Depending on the size of the nozzle and boom, and the ratio of complex alkyl to acid, the expansion rates were consistently found to be about 5.5 to 6.5, and even as high as 8.5. Surprisingly, the foam produced by the hollow cone spray nozzle was in the form of a fine mist that not only had a high cooling efficiency, but also reacted with the flame. It was indeed surprising to consistently obtain foam with expansion rates greater than 5.0.

[0225] We now report on two tests with a 28 square foot tank fire of 10 gallons of E0 gasoline and 1 inch of water at the NRL Fire Test Center in Chesapeake, Md. The test followed the official MILSPEC test protocol using 10 gallons of E0 gasoline but with one modification. Instead of the MILSPEC nozzles, the foam was manufactured and applied with a pressure washer connected to a Torq Foam System cannon and boom of 12 ConeJet Visio Flow hollow cone jet nozzle TX-26 as described previously. The first solution tested was formed from 26,400 g H2O, 60 g xanthan gum, 96 g glycol ether EB and 200 g PPA reacted with 400 g Makon UD5 and then with DETA, having a pH near 7.0. The expansion ratio was about 8. The knockdown time was 31 seconds, very close to the 30 seconds required for AFFF MILSPEC. The reignition time was found to be greater than 12 minutes, while the test requirement was only 360 seconds. The second FFF solution tested was formed from 26,400 g H2O, 60 g xanthan gum, 96 g glycol ether EB and 250 g 98% sulfuric acid reacted with 350 g Makon UD5 and then with 250 g 98% sulfuric acid of DETA, having a pH near 7.0. The expansion ratio was about 8. The knockdown time was 35 seconds, very close to the 30 seconds required for AFFF MILSPEC. The reignition time was found to be greater than 12 minutes. The reignition test was stopped at 12 minutes because the gasoline fuel in the pan was used up. The tank fire did not reignite on the tank. The chief test director at NRL pointed out that the reignition behavior was the best behavior measured in their test laboratory, exceeding the reignition behavior of AFFF. In addition, the 31 second and 35 second knockdown times were much better than the 55 seconds or more usually observed for FFF prepared by other companies at that test site. The superior reignition behavior is attributed to the use of PNS-F with inherent fire retardant properties, resulting in better thermal stability. The fire retardant properties should be related to better thermal stability measured in the gas oven test. Better thermal stability should result in the foam not breaking up as easily and help to shorten the knockdown time. These results confirm that the spray from PNS-F with large coverage area overcomes the low diffusion coefficient inherent to FFF. The results were comparable using PPA or sulfuric acid. The operator found it necessary to move the spray around the tank quickly to get uniform application of the foam blanket. The test with 10 gallons of E0 gasoline required nearly complete blanket formation and extinguishment of the fire. The mist seemed to cool the fire rapidly because the heat felt at a distance of 30 feet rapidly dissipated after the first 15 seconds. These compositions can serve as guidelines. Those familiar with FFF will figure out how to improve the overall behavior by reducing the reignition properties and shortening the knockdown time. For example, perhaps the amount of thickening agent can be reduced.

[0226] When the first solution was sprayed onto the fire in a single stream using the MILSPEC nozzle, the test was abandoned at 30 seconds. It was clear that the extinguishment time would not approach the 31 seconds or 35 seconds obtained using the same FFF solution. This result further demonstrates the power of large area application using atomizing nozzles compared to a single stream. The difficulty in applying foam as a mist is the reduction in expansion ratio due to the wire mesh and hollow cone atomizing nozzle. The superior foaming ability of PNS-F allows it to be used as a foam mist.

[0227] Experts in the FFF field can know how to add or substitute PNS-F into the chemical mixture that forms FFF. Adding a silicone surfactant can help with spreading but will sacrifice other properties. The PNS-F foam forms so effective mist-like foam droplets that these are unexpected properties.

[0228] The Teflon-like compounds are very good conductors of heat. We expect that AFFF foam containing Teflon-like compounds will conduct heat more easily than the PNS-F compounds that expand when heated. If it were not for the lower spreading coefficient of the PNS-F foam than AFFF, the PNS-F compounds can produce a better performing foam than AFFF. However, this problem can be overcome with large coverage area applications.

[0229] A boom was attached to the MILSPEC nozzle. Unfortunately, the solution flowed back and no foam was formed. It would be necessary to improve the dispersion cone in the MILSPEC nozzle to resemble the dispersion wire mesh screen of the foam cannon. Then, the MILSPEC nozzle with a boom attached can be used for FFF testing on fuel tank fires and provide a larger coverage area. Our results show that the performance of FFF requires large coverage area application.

[0230] We found that the hollow cone nozzles produce a finer mist of foam that impinges more gently on the tank surface than the flat fan nozzles or single stream sprays. Thus, for gasoline tank fires, we found less surface splashing with the fine mist hollow cone nozzles. The cooling provided by the hollow cone fine mist extinguishes liquid fuel fires more quickly. Surprisingly, the fine mist nozzles did not break the foam bubbles but produced a foam of small bubbles and the expansion ratio was still over 5, which is the requirement of the MILSPEC test. The fine mist reacts with the free radicals in the flame and cools the flame.

[0231] Many types of testing have been performed with the goal of passing MILSPEC testing without the use of fluorinated compounds. The selection of preferred compositions will be guided by the results of 28 square foot tests with 10 gallons of gasoline. The weight ratio of Makon DA 4 or Makon UD 5 to PPA or SA is preferably 250 / 50 to 150 / 150, more preferably 225 / 75 to 175 / 125. DETA is preferred as the EA for the reaction. We require that such compositions, if applied with a boom using hollow cone nozzles, should be able to have a MILSPEC burn time of less than 40 seconds and a backfire of greater than 360 seconds. The preferred situation will change as different amounts of alcohol ethoxylated and different ethoxylated alcohols are investigated. It appears that alcohols ethoxylated with EO=4 are similar to EO=5. Makon UD2 and Makon UD3 (EO2 and 3) can be helpful, but have not been found in commercial sources. Similar compositions are expected for other ethoxylated alcohols. This range has been investigated only for gasoline fire fighting foam applications. For other fuels such as diesel, for wild fires, and for polymers, the preferred situation can change. More generally, for all uses, the weight ratio of complex alkyl compound to acid is at least 0.01 but less than 20, and reacted with ethylene diamine DETA.

[0232] This testing shows that FFF foams made from polyphosphoric acid or sulfuric acid (SA), DETA, ethoxylated alcohol, and thickener provide a preferred fire fighting foam composition without the need to include an organic solvent such as glycol ether. The company that provides the ethoxylated alcohols Makon DA series and Makon UD series, such as Stepan, also provides thickeners that are compatible with liquid detergents. Liquid detergents are concentrated because the consumer adds water that easily mixes with the detergent. These thickeners can be suitable for our formulations. For example, there are: Biosoft TA2, which is a tallow amine ethoxylate, Stepan Mild GCC, which is glyceryl caprylate / caprate made from glycerol esterified from plant sources, AMPHOSOL CS-50, cocamidopropyl hydroxysultaine, which is an amphoteric surfactant that can be used as a co-surfactant to provide foam enhancement and viscosity increase, and the list of other available products is long. Other companies have introduced new thickeners that are compatible with surfactants. All of these thickeners are candidates to replace Diutan and xanthan gum, or to be used in combination in specific applications of fire fighting foams.

[0233] The complex alkyl phosphate ester solution (CA-PPA) or complex alkyl sulfate solution is formed by reacting a complex alkyl compound with phosphoric acid or sulfuric acid at a temperature that will allow the reaction to form a solution and the weight ratio of complex alkyl to acid is at least 0.01 but less than 20. The formation of the complex alkyl phosphate ester solution requires the PPA to react with the complex alkyl to form a solution that has a little color but is clear in thin film form. Heat accelerates the reaction rate and is necessary to extract the product, which can be very viscous for compositions that are primarily EAPPA. It has been found that using a temperature of 400°F is convenient. For some complex alkyl compounds, lower temperatures can be used and even no heat is possible. Those familiar with the chemistry can start without heat and then adjust the heat to find the best balance of temperature and time to fully form the solution and have a good viscosity to extract the composition from the reactor. The disadvantage of using little or no heat is that it takes longer for the reaction to go to completion and it is very difficult to extract the product. For fast production of CA-SA compositions with acceptable flow properties, no heat has been found to be acceptable. The performance of CA-PPA and CA-SA as fire extinguishing foam is similar. PPA is a weaker acid and is more environmentally friendly. The considerations and preferred compositions of the complex alkyl reacting with phosphoric acid or sulfuric acid will be similar. The fire tests required are very stringent so neither phosphoric acid nor sulfuric acid can be mabe. We have good reason to expect that both acids will produce good performing foam.

[0234] The preferred fatty alcohols and ethoxylated alcohols for the CA-PPA, CA-PA, CA-SA, CASE-PPA, and CAPE-PPA solutions have 8 to 18 carbon atoms, more preferably 9 to 15 carbon atoms, and most preferably 8 to 11 carbon atoms. The degree of ethoxylation depends on the application. The pH of the CA-PPA, CA-PA, CA-SA, CASE-PPA, and CAPE-PPA solutions at 10% by weight in water is preferably less than 2, more preferably less than 1.9, and most preferably less than 1.8, which distinguishes the product from commercial complex alkyl phosphate esters that typically have a pH above 2-2.5. In all the examples in this specification, the solution is reacted with DETA unless otherwise noted. When so many different examples are given in detail in this specification, it is also possible to omit ingredients.

[0235] There are three main application areas: wild fires, foam for fuel fires (especially fuel tank fires), and polymers. For Class A fires, it has been shown in the pct / us20 / 52061 application that a fine mist of PNS is effective for extinguishing Class A fires by spraying into the flame or coating the fuel in front of the flame. As a foam composition with encapsulated soap properties or as a wetting agent that increases adhesion to fuel. The goal is to add some surfactant behavior to the PNS, resulting in a PNS doped with a blowing agent. This is achieved by adjusting the ratio of complex alkyl to PPA in the formation of the complex alkyl polyphosphate (CA-PPA) solution. For Class A fires, the weight ratio of complex alkyl to PPA is less than 0.6, more preferably less than 0.35, most preferably less than 0.15 but greater than 0.01. Such a ratio means that the composition is primarily PNS doped with a small amount of a solution of ethylene amine complex alkyl polyphosphate. The purpose of the complex alkyl is to increase surfactant behavior to more effectively coat the fuel with this PNS-F formulation. Depending on the situation and the size of the fire, a fine mist is sprayed on the fuel in front of or near the fire. For Class A, the aqueous solution concentration is preferably at least 15%, more preferably a concentration of at least 25%, most preferably at least 35%. For Class A applications, ethylene amine that reacts with CA-PPA or CA-PA is preferred. More preferred is ethylene amine that reacts with CA-PPA. The preferred ethoxylation is from 2 to 12, more preferably from 4 to 12, most preferably from 4 to 10.

[0236] It is known that surfactants formed from ethylene amine complex alkyl polyphosphate solution compositions or ethylene amine complex alkyl sulfate solution and their foam solutions are stable in solutions containing sodium chloride. Therefore, FFFs can be prepared with these new surfactants in water or seawater.

[0237] The main ingredient of Purple-K fire extinguishing powder is potassium bicarbonate (78-82% by weight). It is expected that our FFF will be compatible with Purple-K, as it is resistant to sodium chloride and potassium chloride salts.

[0238] Patents US 713844 and US 10501602 show that DETAPPA can be formed in solutions containing large amounts of sodium chloride. Therefore, the new PNS-F surfactants should also be stable in sodium chloride solutions. Therefore, FFF foams prepared with PNS-F can be used in well water or seawater. Well water contaminated with minerals and some kind of dirt was used in all examples.

[0239] For Class B flammable liquid fires, the FFF containing the ethylene amine complexed alkyl polyphosphate solution composition or ethylene amine complexed alkyl sulfate solution is sprayed into the fire to build up on the surface to form a partial covering that helps to smother the fire and provide backdraft protection. The ratio of complexed alkyl to PPA or SA is selected to provide a foaming composition that has some fire retardant properties. For ethylene amine complexed alkyl polyphosphate solutions, the weight ratio of complexed alkyl to PPA or SA is greater than 0.2, more preferably greater than 0.5, most preferably greater than 0.8 but less than 20.0. The preferred pH is from 4 to 9, more preferably from 5.5 to 8.5, most preferably from 6.5 to 7.7. The expansion ratio of the foam is preferably at least 3, more preferably at least 5.0, most preferably at least 6.0 but less than 10.5. The preferred ethoxylation is from 3 to 12, more preferably from 4 to 10, most preferably from 5 to 9. The expansion ratio will vary depending on the equipment used to create the foam.

[0240] A composition that performs well in the 1 square foot and bucket tests does not necessarily perform well in the 28 square foot and 4 gallon gasoline tests. A good performance in the 28 square foot and 4 gallon gasoline tests does not necessarily indicate success in a 10 gallon gasoline or even larger fire such as a 50 square foot or 400 square foot fire. But a poor result in the 1 square foot or bucket test is a strong indicator that it is not worth testing in a larger test. Thus, the preferred composition ranges defined herein can narrow as the tests become more rigorous. Thus, the preferred ranges can narrow. The ability to withstand burn through and achieve backdraft protection can only be tested in truly large fire scenarios.

[0241] For fire retardant polymers, the considerations are different. It is important to use a PPA that has been condensed to a high molecular weight prior to making the complexed alkyl polyphosphate solution. Then, the ethylene amine is reacted with the complexed alkyl polyphosphate solution (CA-PPA). Another option is to form the ethylene amine complexed alkyl polyphosphate solution and then condense it to a high molecular weight form.

[0242] The preferred composition for flame retardant polymers is to add the anhydrous ethylene amine complexed alkyl polyphosphate composition. The weight ratio of complexed alkyl to PPA is preferably at least 0.01 but less than 20, more preferably 0.07 to 1.7, most preferably 0.10 to 1.4. This range is not very narrow because different polymers have different properties, such as thermal stability. Some applications in wire and cable require very high moisture resistance. The preferred pH is 4 to 7.5, more preferably 5.5 to 7.5, most preferably 5.5 to 7. The purpose of the complexed alkyl is to increase the moisture resistance, which depends on the polymer and the application. Ethoxylation has a large effect on the moisture resistance. The preferred ethoxylation is 0-12, more preferably 0-6, most preferably 0-3. 0 means no ethoxylation, such as DETA(LP-PPA).

[0243] For all synthetic cases, the reaction between PPA and the ethoxylated alcohol becomes easier with increasing degree of ethoxylation, and lower temperatures can be used to form the complexed alkyl polyphosphate solution. Therefore, temperatures of 100°F to 450°F should cover all cases, with 200°F to 400°F being more preferred, and 300°F to 400°F being most preferred, to facilitate the reaction between 115% PPA and the complexed alkyl compound, and to easily extract the product from the mixer. The use of lower molecular weight PPA will lower the preferred temperature range to facilitate the reaction. The reaction parameters should be similar for the formation of the complexed alkyl phosphate solution. The term complexed alkyl compound encompasses both ethoxylated and non-ethoxylated compounds.

[0244] For polymer applications, the reaction should be run without solvent or water. This process forms the flame retardant composition to be added to the polymer in one synthesis. The reaction temperature is such that the reaction of the acidic compound with the EA is complete, and the product can be extracted. It is preferred to use only condensed polyphosphoric acid because the high molecular weight is necessary in making the CA-PPA suitable for polymers. Condensation is necessary to reduce the amount of phosphoric acid, making the product as thermally stable as possible.

Claims

1. A chemical precursor solution, comprising chemical precursor solution 1 and chemical precursor solution 2, wherein, The chemical precursor solution 1 is formed by reacting a complex alkyl compound with an acid selected from the group consisting of polyphosphoric acid (PPA), phosphoric acid, sulfuric acid, and sulfonic acid, wherein the weight ratio 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 reacting a complex alkyl sulfate ester formed by reacting the complex alkyl compound with sulfuric acid or a complex alkyl phosphate ester formed by reacting the complex alkyl compound with phosphoric acid with polyphosphoric acid, wherein the weight ratio 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; the complex alkyl compound is selected from the group consisting of ethoxylated fatty alcohols, fatty alcohols, ethoxylated phenols, ethoxylated alkylphenols, and alkyl polysaccharides.

2. The chemical precursor solution according to claim 1, wherein, The reaction to form the chemical precursor solution according to claim 1 is carried out at a temperature between room temperature and 400°F, the polyphosphoric acid grade is 105% to 118%, the concentrations of the phosphoric acid and the sulfuric acid are each at least 80%, and the pH of the 10% by weight aqueous solution of the chemical precursor is less than 2.

2.

3. The chemical precursor solution according to claim 1, wherein, The pH value of a 10% by weight aqueous solution of the chemical precursor is less than 2.

0.

4. A surfactant composition, wherein, The surfactant composition is formed by reacting one or more compounds selected from the group consisting of ethyleneamine, alkali metals, ammonia, and alkanolamines with 1) one or more chemical precursor solutions according to claim 1 and 2) one or more compounds selected from the group consisting of complex alkyl phosphates, complex alkyl sulfates, and complex alkyl sulfonates, wherein the complex alkyl phosphates, the complex alkyl sulfates, and the complex alkyl sulfonates are formed by reacting complex alkyl compounds with phosphoric acid, sulfuric acid, and sulfonic acid, respectively; 10% by weight of the surfactant composition has a pH of at least 3.5 and less than 8.5 in water or in water and organic solvents.

5. The surfactant composition according to claim 4, wherein, The ethylenediamine is selected from the group consisting of ethylenediamine (EDA), diethylenetriamine (DETA), piperazine (PIP), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), and pentaethylenehexamine (PEHA); the complex alkyl phosphate is selected from the group consisting of fatty alcohol phosphates and ethoxylated fatty alcohol phosphates; the complex alkyl sulfate is selected from the group consisting of fatty alcohol sulfates and ethoxylated fatty alcohol sulfates; the complex alkyl sulfonate is a fatty alcohol sulfonate, wherein the ethoxylated fatty alcohol or fatty alcohol has 8 to 18 carbon atoms.

6. A surfactant solution, wherein, The surfactant solution is formed by: 1) dissolving the surfactant composition according to claim 4 in water or in a mixture of water and an organic solvent, wherein the concentration of the surfactant composition is at least 1 wt% of the surfactant solution; or 2) dissolving the chemical precursor solution according to claim 1 in water or in a mixture of water and an organic solvent, and then reacting the chemical precursor solution 1 or the chemical precursor solution 2 with one or more compounds selected from the group consisting of ethyleneamine, alkali metals, ammonia and alkanolamines, wherein the concentration of the resulting surfactant is at least 1 wt% of the surfactant solution.

7. The surfactant solution according to claim 6, wherein, The ethylenediamine is selected from the group consisting of ethylenediamine (EDA), diethylenetriamine (DETA), piperazine (PIP), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), and pentaethylenehexamine (PEHA); the chemical precursor solution is selected from the group consisting of 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.

8. A fluorine-free foam (FFF) composition comprising water and a surfactant solution according to claim 6 or 7, wherein, The pH value of the fluorine-free foam solution is at least 5.5 and less than 8.

5.

9. The fluorine-free foam composition according to claim 8 further comprises 0.1% to 4% by weight of a thickener selected from the group consisting of fumed silica, xanthan gum, diurtan, stearin, heteropolysaccharides, locust bean gum, partially hydrolyzed starch and guar gum; and further comprises 0.1% to 4% by weight of an organic solvent.

10. The fluorine-free foam composition according to claim 9, wherein, The organic solvent is a glycol ether, selected from the group consisting of 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; the organic solvent includes any propylene oxide-based material.

11. The fluorine-free foam composition according to claim 10, 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 tert-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.

12. The fluorine-free foam composition according to any one of claims 8 to 11, wherein if the compound selected to react with the acid is ethyleneamine, the fluorine-free foam composition has foaming agent properties and flame retardant properties.

13. A mixture of a surfactant and ethylamine polyphosphate (EAPPA), wherein, The surfactant is a surfactant composition according to claim 4 or 5, a surfactant solution according to claim 6 or 7, or a fluorine-free foam composition according to any one of claims 8 to 12, and the amount of the ethylenediamine polyphosphate is from 1% to 99% by weight of the mixture.

14. A mist-like, water-based, fluorine-free fire extinguishing foam (FFF), comprising the fluorine-free foam composition according to any one of claims 8 to 12, wherein the water-based, fluorine-free fire extinguishing foam has an expansion rate greater than 2 but less than 20 and a water content of at least 45% but less than 99%, wherein, The mist is composed of droplets with a median diameter of less than 1500 micrometers, or less than 600 micrometers, or less than 400 micrometers, or less than 200 micrometers, or less than 75 micrometers.

15. The water-containing fire extinguishing fluorine-free foam according to claim 14, wherein, The mist is delivered by a system comprising a Venturi-type foam former having at least one boom having at least two nozzles extending into the flame, the system's operating variables and the composition of the water-based fire extinguishing fluorine-free foam being such that a mist of the water-based fire extinguishing fluorine-free foam with an expansion rate of at least 3 is discharged.

16. The water-containing fire extinguishing fluorine-free foam according to claim 15, wherein, The expansion ratio is at least 5, and the foam is made of water or seawater.

17. The water-containing fire extinguishing fluorine-free foam according to claim 16, wherein, The mist is discharged by a boom configured to cover at least 25% of the fire's surface area.

18. The water-based, fluorine-free fire extinguishing foam according to any one of claims 14 to 17, wherein, The mist-like, water-containing, fluorine-free fire extinguishing foam has the ability to cool the flame and react with flame plasma free radicals and ions.