Fire extinguishing composition

Abstract

The fire extinguishing concentrate comprises water, a first surfactant that is an anionic surfactant, a second surfactant that is an amphoteric surfactant, a third surfactant selected from the group consisting of anionic surfactants and amphoteric surfactants, and water, and optional ingredients, the third surfactant is different from the first surfactant and the second surfactant. The concentrate can be combined with water to provide a fire extinguishing composition that can be applied to fire in a time and amount effective to extinguish fire.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application is a divisional application of Chinese Patent Application No. 201580020119.8, and claims the benefit of U.S. Provisional Patent Application No. 61 / 941,396 filed on February 18, 2014, which is incorporated herein by reference in its entirety. Technical Field

[0003] The present invention generally relates to fire extinguishing compositions, concentrates thereof, and methods of making and using the compositions. Background Art

[0004] Uncontrolled fire is one of the most dangerous and undesirable events faced by people. Therefore, there is a need for fire extinguishing compositions that effectively extinguish flames in a short period of time. It is highly desirable that those compositions are non-toxic to the environment, and if they come into contact with humans, it is certainly desirable that they are harmless to humans. Likewise, it is highly desirable that the combustion products of those compositions are generally non-toxic to the environment and harmless to human and animal life. The present invention is directed to achieving these and related needs related to extinguishing uncontrolled flames. Summary of the invention

[0005] Briefly stated, the present disclosure provides fire extinguishing concentrates, fire extinguishing compositions in water-diluted forms of the concentrates, methods of making the concentrates and compositions, and methods of using the concentrates and compositions to extinguish fires.

[0006] In one embodiment, the present disclosure provides a composition comprising water and a solid, wherein the solid comprises a first surfactant selected from an amphoteric surfactant, a second surfactant selected from an anionic surfactant, and a third surfactant selected from an amphoteric surfactant and an anionic surfactant, wherein the third surfactant is different from the first surfactant and the second surfactant. The composition can be used directly for fire extinguishing, or it can be prepared in a concentrated form, which can be diluted as needed to provide a fire extinguishing composition. The composition or its concentrate can include one or more optional ingredients. Exemplary optional ingredients are inorganic salts, organic solvents, and thickeners.

[0007] In another embodiment, the present disclosure provides a composition comprising water and a solid, wherein the solid comprises a first surfactant selected from an amphoteric surfactant, and a second surfactant selected from an anionic surfactant. The composition can be used directly for fire extinguishing, or it can be prepared in a concentrated form, which can be diluted as needed to provide a fire extinguishing composition. The composition or its concentrate can contain one or more optional ingredients. Exemplary optional ingredients are inorganic salts, organic solvents and thickeners.

[0008] In one embodiment, the present disclosure provides a method for preparing a fire extinguishing concentrate by an intermittent processing method. In this embodiment, the fire extinguishing concentrate composition is prepared by a method comprising: adding hot water, anionic surfactants, amphoteric surfactants, and a third surfactant optionally selected from anionic surfactants and amphoteric surfactants to a container, wherein the third surfactant is different from the anionic surfactants and amphoteric surfactants that have been added. Other optional ingredients include inorganic salts, organic solvents, and thickeners; wherein after adding the components to the container, before adding the next component, the resulting mixture is stirred until it reaches a completely or almost uniform state, for example, for about 30 minutes, wherein a minimum amount of foam is generated.

[0009] For example, the present invention provides a method for preparing a fire extinguishing concentrate composition, comprising:

[0010] a) heating water to about 70-80° C. to provide hot water;

[0011] b) adding anionic surfactant to the hot water;

[0012] c) adding an amphoteric surfactant to the mixture of step b);

[0013] d) adding hot water to the mixture of step c);

[0014] e) optionally, adding a third surfactant to the mixture of step d), said third surfactant being selected from anionic surfactants and amphoteric surfactants, said third surfactant being different from the anionic surfactants and amphoteric surfactants already present in said mixture;

[0015] f) adding an inorganic salt to the mixture of step e);

[0016] g) cooling the mixture of step f) to ambient temperature; and

[0017] h) adding a thickener to the mixture of step f);

[0018] After adding a component, the resulting mixture is stirred for a time effective to obtain a homogeneous or nearly homogeneous mixture, generally about 30 minutes, with a minimum of foaming, prior to adding the next component.

[0019] In one embodiment, the present disclosure provides a method for preparing a fire extinguishing concentrate by a continuous process. In this embodiment, the fire extinguishing concentrate is prepared by: providing a continuous reactor, injecting water into the continuous reactor, adding a) anionic surfactant, b) amphoteric surfactant and c) a third surfactant optionally selected from anionic surfactants and cationic surfactants to the water in the continuous reactor, wherein the third surfactant is different from the anionic surfactant and amphoteric surfactant already injected into the reactor; and mixing components a), b) and optionally c) to provide a uniform mixture. Optionally, the water in the continuous reactor is maintained at a temperature exceeding 50°C. Optionally, other ingredients such as organic solvents, inorganic salts and thickeners are added to the formulation. Optionally, a mixer selected from an inline mixer and a static mixer is present in the continuous reactor.

[0020] In one embodiment, the present disclosure provides a method for forming a fire extinguishing composition from a fire extinguishing concentrate. According to this embodiment, water and concentrate are combined in a suitable water:concentrate ratio, and the two components are mixed together to form the fire extinguishing composition. The mixing can optionally be achieved by means of a venturi tube, wherein the diameter of the tube through which the water flows is restricted so that the concentrate enters the water from the reservoir to provide the fire extinguishing composition.

[0021] In one embodiment, the present disclosure provides a method of extinguishing a fire, wherein the method comprises applying an effective amount of a fire extinguishing composition of the present disclosure to the fire for a time effective to extinguish the fire.

[0022] The following description sets forth the details of one or more embodiments. The features set forth or described in connection with an exemplary embodiment may be combined with the features of other embodiments. Other features, objects, and advantages will be apparent from the specification and claims. In addition, the disclosures of all patents and patent applications referenced herein are incorporated by reference in their entirety. DETAILED DESCRIPTION

[0023] In one aspect, the present disclosure provides fire extinguishing compositions in concentrated form and in diluted form (ready to use). In another aspect, the present disclosure provides methods of forming a fire extinguishing composition in concentrated form and then diluting the concentrated composition into a diluted form. In another aspect, the present disclosure provides methods of using the composition as a means of fire extinguishing.

[0024] In short, except carrier, described composition comprises at least two kinds of active ingredients, and optionally comprises at least three kinds of active ingredients.Those compositions are amphoteric surfactant and anionic surfactant, and when there is the third surfactant, this third surfactant is selected from anionic surfactant and amphoteric surfactant, and it is different from described first (amphoteric) surfactant or described second (anionic) surfactant.Described composition can comprise one or more optional ingredients, for example, inorganic salt and thickening agent.Carrier is water, optionally it is combined with a small amount of organic solvent.On the one hand, fire extinguishing composition does not comprise carbon-halogen bond, therefore it is more friendly to environment than the alternative composition comprising one or more components with this type of bond.

[0025] Note that, as used in this specification and the claims intended to be protected, the singular forms "a", "an", and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "an amphoteric surfactant" includes a single amphoteric surfactant as well as one or more of the same or different amphoteric surfactants.

[0026] Components

[0027] Amphoteric surfactant

[0028] The fire extinguishing composition of the present disclosure comprises at least one amphoteric surfactant, and optionally comprises a plurality of amphoteric surfactants. As used herein, an amphoteric surfactant is a molecule that contains both positively charged atoms and negatively charged atoms. The surfactant molecule may contain a polymer component, and may also include counterions such as sodium and ammonium, but the counterion is not considered to be one of the positively or negatively charged atoms that makes the molecule an amphoteric surfactant.

[0029] The positively charged atom can be, for example, a nitrogen atom providing an ammonium group, or can be a sulfur atom providing a sulfonium group. The presence of a positive charge on a particular atom can vary with changes in the pH to which the molecule is exposed. In other words, the amphoteric surfactants of the present disclosure do not need to contain both positively charged atoms and negatively charged atoms at each pH of the surrounding solution, but can contain these charged atoms only within a pH range. For example, when a molecule contains a positively charged nitrogen atom, the charge can only exist when the pH of the surrounding solution (aqueous solution) is sufficiently low (the nitrogen atom becomes protonated). For example, this occurs when the nitrogen atom is part of a primary amine, a secondary amine, or a tertiary amine. Alternatively, the nitrogen atom can be part of a quaternary ammonium ion that maintains its positive charge regardless of the pH of the surrounding solution.

[0030] Negatively charged atoms can be, for example, oxygen atoms that can be part of a recognized functional group (e.g., carboxylate, sulfate, sulfonate or phosphate). Like positive charges, the presence of negative charges on specific atoms can vary with changes in the pH to which the molecule is exposed. In other words, the amphoteric surfactants of the present disclosure do not need to contain negatively charged atoms and positively charged atoms at each pH of the surrounding solution, but can contain these charged atoms only within the pH range. For example, when a molecule contains negatively charged oxygen atoms, the charge can only exist when the pH of the surrounding solution (aqueous solution) is high enough (the oxygen atom becomes deprotonated). For example, this can occur when the oxygen atom is, for example, a part of a carboxylic acid group, wherein only the carboxylate form of the carboxylic acid group contains negatively charged oxygen atoms, and the corresponding carboxylic acid form contains neutral oxygen atoms.

[0031] In summary, amphoteric surfactants do not need to contain both positively charged atoms and negatively charged atoms in all possible pH ranges of the surrounding solution, but will contain these two charged atoms in some pH ranges, which are sometimes referred to as isoelectric pH ranges in the art. When amphoteric surfactants contain both positively charged atoms and negatively charged atoms, it can be said that the surfactant is in its zwitterionic form. When the chemical structure of amphoteric surfactants is provided herein, the term X can be used to refer to the counter ions that may be associated with positively or negatively charged atoms in the isoelectric pH range. Exemplary cationic counter ions are sodium and ammonium. Exemplary anionic counter ions are chlorine and phosphate. It is worth noting that the positive charge or negative charge can be delocalized in multiple atoms. For example, when the negative charge is on an oxygen atom and the oxygen atom is part of a carboxylate, the negative charge is delocalized in two oxygen atoms of the carboxylate.

[0032] In addition, and like all surfactants, amphoteric surfactants will contain lipophilic (also known as hydrophobic) regions and lipophobic (also known as hydrophilic) regions. The lipophilic region can be referred to as the fatty region. The fatty region can be composed of hydrocarbon moieties, which are present in naturally occurring fatty acids, fatty alcohols, fatty amines, etc., but they can alternatively be formed by synthesis, that is, they can be synthetically produced fragments such as polyethylene, polypropylene, poly(propylene oxide), etc. As used herein, and when describing a class of amphoteric surfactants, the term "R" will be used to refer to the fatty region of the molecule. In various embodiments, R represents a medium-chain or long-chain aliphatic group, such as: C6-C 24 A fragment, i.e., a molecular fragment containing at least 6 and up to 24 carbon atoms and optionally any other atoms (e.g., hydrogen, halogen (e.g., F, Cl, Br), nitrogen and oxygen); C6-C 24 Hydrocarbons, i.e., molecular fragments containing 6-24 carbon atoms and sufficient hydrogen atoms to complete the valence of the carbon atoms; C8-C 22Fragment; C8-C 22 Hydrocarbon; C 10 -C 20 Fragment; C 10 -C 20 Hydrocarbon; C 12 -C 18 fragment; and C 12 -C 18 Hydrocarbon. In different embodiments, R contains at least 6, or at least 8, or at least 10, or at least 12, or at least 14, or at least 16 carbon atoms. In different embodiments, R contains no more than 30, or no more than 26, or no more than 24, or no more than 22, or no more than 20, or no more than 18 carbon atoms. The term R can represent an alkyl group, wherein the term alkyl refers to a straight chain, a branched chain, or a cyclic saturated hydrocarbon group, which usually contains any number of carbon atoms in the above specified carbon atom range (for example, C6-C24 refers to an alkyl group containing 6 to 24 carbon atoms). Examples of alkyl groups include 3-methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, caprylic acid group, capric acid group, lauric acid group, myristic acid group, palmitic acid group, stearic acid group, oleic acid group, linoleic acid group, linolenic acid group, and behenic acid group.

[0033] Several paragraphs below provide examples of exemplary specific surfactant classifications and specific amphoteric surfactants that can be incorporated into the fire extinguishing composition of the present disclosure. It should be noted that the classifications are not mutually exclusive, because a specific amphoteric surfactant can fall into multiple classifications, that is, two classifications can overlap in terms of the surfactants covered by the classification. The surfactant field uses different nomenclatures to classify and identify amphoteric surfactants in particular and types of surfactants in general, wherein the nomenclatures do not generally provide classifications of surfactants that are mutually exclusive. However, the following provides amphoteric surfactants for use in the present disclosure. For convenience, surfactants can be identified with reference only to their charged portions. For example, an amphoteric surfactant can be referred to as a betaine or betaine surfactant to indicate that the amphoteric surfactant contains a betaine group. As another example, when an amphoteric surfactant contains a hydroxysulfonyl betaine group, such a surfactant can be referred to as a hydroxysulfonyl betaine surfactant, or when the context permits, even more simply as a hydroxysulfonyl betaine. Alternatively, it can be said that an amphoteric surfactant contains a clearly identified charged group, such as a betaine or betaine group, a hydroxysulfonyl betaine group, an amine oxide group, and the like.

[0034] In some of the following chemical structures, the term "L" is used to refer to a linking group. A linking group is a short chain of atoms that connects two significant functional groups present in an amphoteric surfactant. In one embodiment, L is a methylene group, i.e., -CH2-. In one embodiment, L is an ethylene group, i.e., -CH2CH2-. In one embodiment, L is a propylene group, i.e., -CH2CH2CH2-. The linking group may include a substituent on the alkylene chain, wherein the substituent may be, for example, a halogen, a hydroxyl, or a short chain (about C1-C4) alkyl. In one embodiment, L is a propylene group substituted with a hydroxyl group, e.g., -CH2CH(OH)CH2-. In another embodiment, L is a methylene group substituted with a methyl group, e.g., -CH(CH3)-. In one embodiment, L is a methylene group, an ethylene group, or a propylene group, each optionally substituted with a hydroxyl group. In one embodiment, L is dimethyl ether, i.e., -CH2-O-CH2-. In one embodiment, L is a chain of 1-5 atoms selected from carbon and oxygen, wherein the chain is optionally substituted with hydroxy or halide.

[0035] Any of the following terms may be used to expressly state "amphoteric surfactants" to thereby provide a selection of amphoteric surfactants for use in embodiments of the present disclosure: alkylamidopropyl betaines, alkylamine oxides, alkyl amphoacetates, alkyl betaines, alkyl carboxyglycinates, alkyl glycinates, alkyl sultaines, sultaines, alkyl amphopropionates, alkyl amphoglycinates, alkylamidopropyl hydroxysultaines, acyl taurinates, and acyl glutamates. Each of these terms is known in the art, and many of these terms are described below.

[0036] In one embodiment, the amphoteric surfactant is a betaine surfactant, which means that the surfactant comprises a betaine group. The betaine surfactant can be an alkylamidopropyl betaine, which can be represented by the chemical structure CH3-(C H2) when the alkyl group is a linear alkyl group. n -CONH-CH2CH2CH2-N(CH3)2-CH2-COOX. More generally, amidopropyl betaine can be represented by the chemical structure R-CONH-CH2CH2CH2-N(CH3)2-CH2-COOX. These are all examples of alkyl amido betaines.

[0037] In one embodiment, the amphoteric surfactant is an alkyl amidosulfobetaine, which can be represented by the chemical structure R-CONH-LN(CH3)2-(CH2) m-SO2OX, wherein L is propylene. A subset of this class is alkylbenzene dimethyl ammonium propanesulfonate obtained by quaternizing alkylbenzene dimethyl amine with propanesulfone. In addition, the propylene linking group L can be substituted, for example, with a hydroxyl group (which provides a 2-hydroxy-1-propanesulfonate derivative) to provide another amphoteric surfactant suitable for use in the compositions of the present invention.

[0038] In one embodiment, the amphoteric surfactant is an alkyl amino acid type amphoteric surfactant, which can be represented by the chemical structure R-NH-L-COOX, wherein R and L are as defined above. For example, R can be derived from coconut oil, L can be ethylene and X can be a sodium ion.

[0039] In one embodiment, the amphoteric surfactant is an alkyl betaine amphoteric surfactant, which can be represented by the chemical structure RN(CH3)2-L-COOX, where R is an alkyl group and L is a linking group. As with other amphoteric surfactants disclosed herein, the R group can be an aliphatic group, not limited to an alkyl group, however, in one embodiment, R represents an alkyl group. As previously described, in one embodiment, the linking group can be a methylene group. However, alkyl betaines also include α-(N,N,N-trialkylammonium)alkanoates, which have the structure R 1 -N(R 2 )(R 3 )-C(R 4 )H-COOX, wherein L is an alkyl-substituted methylene. Various alternative and sometimes more specific names are used to name alkyl betaines, for example, N-alkyl-N,N-dimethylglycine; N-alkyl-N,N-dimethyl-N-carboxymethylammonium betaine; alkyl-dimethylammonium acetate or alkyl-dimethylammonium acetate. The Cosmetic, Toiletry and Fragrance Association, Inc. (CTFA) names these products alkyl-betaines.

[0040] In one embodiment, the amphoteric surfactant is an alkyl imidazoline derived amphoteric surfactant, which can be represented by the chemical structure R-CONH-LN(CH2CH2OH)CH2COONa. In another embodiment, the alkyl imidazoline derived amphoteric surfactant is a diacid, which can be represented by the chemical structure R-CON(CH2CH2OH)-LN(CH2COONa)2. In any of these embodiments, the linker L is optionally ethylene.

[0041] In one embodiment, the amphoteric surfactant is an alkyl imino diacid amphoteric surfactant, which can be represented by the chemical structure RN (CH2CH2COONa) 2. In an alternative embodiment, the alkyl imino diacid amphoteric surfactant is represented by the chemical structure RN (CH2CH2CH2COONa) 2 or RN (CH2COONa) 2.

[0042] In one embodiment, the amphoteric surfactant is an alkyl sulfobetaine amphoteric surfactant. The chemical structure of alkyl sulfobetaine can be expressed as RN(CH3)2-L-SO2OX (sometimes also expressed as -L-SO3X), where R is an alkyl group and L is a methylene group. The following are examples of specific alkyl sulfobetaines that can be used in the practice of the present invention: capryl sulfobetaine, hexadecyl sulfobetaine, lauryl sulfobetaine, myristyl sulfobetaine, n-octyl sulfobetaine, palmityl sulfobetaine, tetradecyl sulfobetaine.

[0043] In one embodiment, the amphoteric surfactant is an alkyl sulfobetaine, which is a CTFA preferred term. Alkyl sulfobetaines are sulfobetaine amphoteric surfactants containing propanesulfonate, i.e., L-SO3X, where L is propylene. Alkyl sulfobetaines have the chemical structure RN(CH3)2-CH2CH2CH2-SO2OX.

[0044] In one embodiment, the amphoteric surfactant is an amidopropyl betaine, which can be represented by the chemical structure R(C=O)-NH-(CH2)3-N(CH3)2-CH2COOX. This type of amidopropyl betaine can also be referred to as an alkylamidopropyl betaine, because R can be an alkyl group. Alkylamidopropyl betaine surfactants are typically synthesized by reacting a fatty acid (e.g., a fatty acid from a natural oil such as coconut oil) with 3,3-dimethylaminopropylamine to provide an amidopropyl dimethylamine intermediate, which is then reacted with sodium monochloroacetate to provide the corresponding betaine. Betaine surfactants are typically named after the source of the fatty acid used to prepare them, for example, coconut oil provides cocamidopropyl betaine, and isostearic acid provides isostearamidopropyl betaine. Many alkylamidopropyl betaine surfactants suitable for use in the present invention are commercially available in solid and solution form and can be purchased from different suppliers.

[0045] The following are specific exemplary amidopropyl betaines that can be used in the practice of the present invention: apricotamidopropyl betaine, betaine), avocado amidopropyl betaine, babassu amidopropyl betaine, behenamidopropyl betaine, canola amidopropyl betaine, capryloyl / capryloyl propyl betaine (formed from a mixture of caprylic and capric acids), coco / oleamidopropyl betaine, coco / sunflower amidopropyl betaine (formed from a mixture of coconut and sunflower oils), theobroma cacao amidopropyl betaine (made from the pulp of the theobroma cacao tree), isostearamidopropyl betaine, lauramidopropyl betaine, limnanthes alba seed amidopropyl betaine (formed from limnanthes alba seed oil), milkamidopropyl betaine, minkamidopropyl betaine (formed from mink oil), myristylamidopropyl betaine, avena sativa amidopropyl betaine (formed from oats (Avena sativa) Sativa) (formed from palm oil), oleamidopropyl betaine, oliveamidopropyl betaine, palmamidopropyl betaine (formed from palm oil), palmamidopropyl betaine, palm kernelamidopropyl betaine (formed from palm kernel oil), ricinoleic acid amidopropyl betaine, sesame amidopropyl betaine, shea amidopropyl betaine (formed from Butyrospermum Parkii (shea butter)), soya amidopropyl betaine, stearamidopropyl betaine, tallowamidopropyl betaine, undecylenamidopropyl betaine, and wheat germ oleamidopropyl betaine (formed from oil in wheat germ).

[0046] In one embodiment, the amphoteric surfactant is an amine oxide amphoteric surfactant, which can be represented by the chemical structure RN (CH ) 2-O-, wherein R is a lipophilic group. Exemplary R groups are lipophilic alkyl groups, wherein the amine oxide surfactant containing R as an alkyl group is generally referred to as an alkylamino oxide. Exemplary alkyl groups are caprylic acid groups, capric acid groups, lauric acid groups, myristic acid groups, palmitic acid groups, stearic acid groups, oleic acid groups, linoleic acid groups, linolenic acid groups and behenic acid groups. Exemplary amine oxide amphoteric surfactants include cocamidopropylamine oxide and lauryl dimethylamine oxide (also known as dodecyl dimethylamine oxide, N, N-dimethyldodecylamine N-oxide and DDAO), soybean oil amide propylamine oxide and myristylamine oxide. The nitrogen atom of the amine group can be bonded to two methyl groups as shown above, however, as an alternative, the nitrogen atom can be bonded to two hydroxyethyl groups to provide the structure RN (CH 2 CH 2 OH) 2-O-.

[0047] In one embodiment, the amphoteric surfactant is an amino acid type amphoteric surfactant. This type of amphoteric surfactant exhibits a zwitterionic structure in certain pH ranges, and the pH range depends on the structure of the surfactant. Common examples of this type of amphoteric surfactant are amino acids of structure R-NH-CH2CH2-COOH, where R is an aliphatic group. These are sometimes referred to as aliphatic amino acids, or more specifically aliphatic aminopropionates when in the form of corresponding carboxylates. A variation of this structure contains two carboxylic acid groups, i.e., has the structure RN(CH2CH2COOH)2, which is named as fatty iminodipropionate when in the form of corresponding carboxylates. Any of these types of amphoteric surfactants can be used in the compositions of the present disclosure.

[0048] In one embodiment, the amphoteric surfactant is an amphoteric acetate amphoteric surfactant, which contains the chemical structure -CH2-CO2X in addition to an aliphatic group and a chemical group that will become positively charged at a suitable pH. These surfactants are sometimes referred to as amphoteric glycinates. In one embodiment, the amphoteric acetate amphoteric surfactant can be represented by the chemical structure R(CO)NH-CH2CH2-N(CH2CH2OH)(CH2CO2X), where R can be an alkyl group or R(CO) can be a fatty acyl group derived from a fatty acid such as found in coconut oil, to provide, for example, coconut oil amphoacetate. Such amphoteric acetate surfactants can be prepared by reacting a compound of formula R(CO)NH-CH2CH2-NHCH2CH2OH with formaldehyde and cyanide as disclosed in U.S. Pat. No. 6,232,496. Under appropriate conditions, this amphoteric acetate can be interconverted into the corresponding amphoteric acetate amphoteric surfactant containing an imidazolium group that provides a positively charged chemical group, such as lauroyl amphoacetate (sodium salt).

[0049] The amphoacetate amphoteric surfactant may contain two acetate groups instead of one to provide an amphoteric surfactant having the chemical structure R(CO)NH-CH2CH2-N(CH2CH2OCH2CO2X)(CH2CO2X). Exemplary amphoacetate amphoteric surfactants include disodium cocoamphodiacetate, sodium cocoamphoacetate, disodium lauroamphoacetate, and sodium lauroamphoacetate.

[0050] In one embodiment, the amphoteric surfactant is amphoteric propionate amphoteric surfactant, which, in addition to comprising an aliphatic group and a chemical group that will become positively charged at a suitable pH, also comprises a chemical structure -CH2CH2-CO2X. Such amphoteric surfactants can be prepared from acrylic acid as described in U.S. Patent No. 6030938. Exemplary amphoteric propionate amphoteric surfactants are sodium capryloyl amphoteric propionate, sodium lauryl iminodipropionate, sodium isostearyl amphopropionate, and sodium cocoyl amphoteric propionate. Amphoteric propionate amphoteric surfactants can include two rather than one propionate radical to provide an amphoteric surfactant with a chemical structure of R(CO)NH-CH2CH2-N(CH2CH2OCH2CH2CO2X)(CH2CH2CO2X). This subclass of zwitterionic propionate zwitterionic surfactants is known as zwitterionic dipropionate zwitterionic surfactants, with exemplary zwitterionic dipropionate zwitterionic surfactants being disodium cocoamphodipropionate (also known as N-(2-cocoamidoethyl)-N-(2-(2-carboxyethyl)oxyethyl)-β-aminopropionic acid, disodium salt) and disodium capryloamphodipropionate.

[0051] In one embodiment, the amphoteric surfactant is a betaine surfactant. Betaine refers to a surfactant molecule that incorporates both a positively charged (cationic) functional group (e.g., a phosphonium or quaternary ammonium group without a hydrogen atom) and a negatively charged (anionic) functional group (e.g., a carboxylate or an oxygen ion). In betaines, the cationic and anionic groups are not adjacent to each other. Betaine surfactants as mentioned herein will meet the above definition and will also contain a lipophilic portion. In one embodiment, the cation is a quaternary amine. In one embodiment, the anion is a carboxylate. In another embodiment, the anion is an oxygen ion. In another embodiment, the anion is a sulfate. In another embodiment, the anion is a sulfonate. In another embodiment, the anion is a phosphate. Many commercially available betaines contain dialkyl-substituted dimethylammonium groups. Although such groups are common in commercial amphoteric surfactants, the amphoteric surfactants that can be used in the present disclosure do not necessarily (although they can) contain dimethylammonium groups. More generally, they contain dialkylammonium groups to provide, for example, a chemical structure of R 1 -N(R 2 )(R 3 )-CH2COOX trialkylammonium alkanoate. In other words, R 2 and R 3It does not have to be methyl. Some exemplary betaines are alkyl dimethyl betaine having the chemical structure RN(CH3)2-CH2-COOH and alkyl amidopropyl dimethyl betaine having the structure R-CONH-CH2CH2CH2-N(CH3)2-CH2-COOH.

[0052] In one embodiment, the amphoteric surfactant is a hydroxysulfonate having the chemical structure RN(CH3)2-CH2CH(OH)-SO3X, wherein R is an aliphatic group, e.g., a long chain alkyl group. Hydroxysulfonates are typically named after the source of the R group, so for example, hydroxysulfonates from coconut oil may be named cocamidopropyl hydroxysulfonate (however, it is also known as coconut hydroxysulfaine and CAHS). Other exemplary hydroxysulfonate amphoteric surfactants include lauroamidopropyl hydroxysulfonate, oleamidopropyl hydroxysulfonate, tallowamidopropyl hydroxysulfonate, erucamidopropyl hydroxysulfonate, and lauryl hydroxysulfonate.

[0053] In one embodiment, the amphoteric surfactant is an imidazoline derivative amphoteric surfactant, which is sometimes referred to as an imidazolinium salt derivative. Due to the fact that imidazoline characteristically hydrolyzes when exposed to water, the chemical structure of the imidazoline derivative amphoteric surfactant becomes complicated. Aliphatic imidazolines slowly hydrolyze when exposed to humid air to produce alkyl amidoamines. Therefore, the alkyl amidoamine amphoteric surfactants described elsewhere in this article are examples of imidazolinium salt derivative amphoteric surfactants. Generally, imidazolinium salt derivative amphoteric surfactants, which are sometimes referred to as imidazoline amphoteric surfactants, are well known in the art as a class of surfactants. In one embodiment, the amphoteric surfactant is an imidazoline derivative, optionally an aliphatic alkyl imidazoline. This type of amphoteric surfactant forms cations in acidic solutions, anions in alkaline solutions, and "zwitterions" in solutions in the neutral pH range. The neutral pH range, also known as the isoelectric point range, in which imidazoline surfactants carry a neutral charge is compound specific and depends on the exact structure of the compound, which will affect the basicity of the nitrogen atom and the acidity of the carboxylic acid group. Exemplary suitable imidazoline-type amphoteric surfactants include, but are not limited to, 2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy disodium.

[0054] Imidazolinium salt derivative amphoteric surfactants can be prepared by the reaction of sodium chloroacetate with the corresponding 2-alkyl-1-(2-hydroxyethyol-)-2-imidazoline. The product of this reaction is generally assigned the following chemical structure:

[0055]

[0056] Wherein R is a hydrophobic group. The reaction to produce these cyclic imidazolinium salt derivatives can be easily extended to provide the corresponding open-chain molecules with the following structures: RCO-NH-CH2CH2-N(CH2CH2OH)CH2COO- (with one equivalent of sodium chloroacetate) and RCO-NH-CH2CH2-N(CH2CH2OH)(CH2COO-)2 (with two equivalents of sodium chloroacetate). Such open-chain structures are generally referred to as imidazoline derivatives, or alkyl (when R is alkyl) amidoamino acids (when a single equivalent of sodium chloroacetate is used for its preparation).

[0057] Commercially available amphoteric imidazolinium salts may be one or more of the foregoing structures, which are suitable for use in the present disclosure. The imidazolinium salt derivative should be selected with some caution, as the same term is used somewhat confusingly to refer to cationic (as opposed to amphoteric) surfactants that incorporate or are prepared from imidazoline, for example, cationic surfactants having the following structure:

[0058]

[0059] Therefore, those skilled in the art sometimes specifically refer to amphoteric imidazolinium salt surfactants to distinguish them from so-called cationic imidazolinium salt surfactants.

[0060] Examples of suitable amphoteric imidazolinium salt derivatives have an R group selected from C6-C22 alkyl groups, for example, caprylic acid group, capric acid group, lauric acid group, myristic acid group, palmitic acid group, stearic acid group, oleic acid group, linoleic acid group, linolenic acid group and behenic acid group.

[0061] In one embodiment, the amphoteric surfactant is a phosphinate betaine amphoteric surfactant. Phosphinate betaines are similar to alkyl betaines and sulfobetaines in which the carboxyl or sulfonic acid groups have been replaced by phosphine groups. Phosphinate betaines can be represented by the chemical structure RN(CH3)2-LP(=O)(R)OX. L can be, for example, propylene.

[0062] In one embodiment, the amphoteric surfactant is a phosphonate betaine amphoteric surfactant. Phosphonate betaines are similar to alkyl betaines and sulfobetaines in which the carboxyl or sulfonic acid groups have been replaced by phosphonate groups. Phosphonate betaines can be represented by the chemical structure RN(CH3)2-LP(=O)(OR)OX. L can be, for example, propylene.

[0063] In one embodiment, the amphoteric surfactant is a pyridinium alkanoate amphoteric surfactant, which can be represented by the chemical structure Wherein R is an aliphatic group, for example, a medium-chain or long-chain alkyl group. However, at a suitable pH, the carboxylic acid (-COOH) group of the pyridinium alkanoate shown in the carboxylic acid form will be converted to a carboxylate (COOX) group.

[0064] In one embodiment, the amphoteric surfactant is a sulfate ion-containing amphoteric surfactant. Sulfate ion groups can be easily added to aliphatic unsaturated amines such as oleylamine (1-amino-9,10-octadecene) to provide the corresponding sulfate ion-containing amphoteric surfactant named 9-(10)-hydroxyoctadecylamine.

[0065] In one embodiment, the amphoteric surfactant is a sulfated betaine, also known as alkyl dimethyl ammonium alkyl sulfate, which can be represented by the chemical structure RN (CH3) 2-L-OSO3X. Sulfated betaine is an example of an amphoteric surfactant that contains a sulfate ion and also contains a betaine group.

[0066] In one embodiment, the amphoteric surfactant is a sulfobetaine amphoteric surfactant. The chemical structure of the base compound can be expressed as RN(CH3)2-L-SO2OX (sometimes also expressed as –L-SO3X). Because they are commercially available, many sulfobetaines have L that is a propylene group, and such amphoteric surfactants can be used in the embodiments of the present disclosure. Sulfobetaine is an example of an amphoteric surfactant that contains a sulfonic acid and also includes a betaine group. Such betaine amphoteric surfactants include ammonium alkanesulfonates and 2-(N-alkyl-N,N-dimethylammonium) ethane sulfonates. Sulfobetaine also includes trialkylammonium compounds that are similar to alkyl betaines but whose carboxyl groups are replaced by alkyl sulfonates. When R is a lipophilic alkyl group, such sulfobetaine can be referred to as an alkyl sulfobetaine. Alkyl sulfobetaine surfactants are generally named after the long-chain alkyl groups present in their structure. For example, when R contains 12 carbon atoms in a direct connection, ie, is lauryl, the corresponding sulfobetaine is called lauryl sulfobetaine.

[0067] There are many sulfobetaine surfactants that are variations of the typical structures shown above. For example, the propylene group specified by "L" can be substituted by different functional groups, for example, halogen, hydroxyl and methoxy. The R group need not be a straight chain alkyl, but can be a branched hydrocarbon or even an alicyclic or aromatic hydrocarbon. In fact, the R group need not even be a hydrocarbon. Mainly, the R group must be lipophilic, and many chemical structures provide this property. Examples of sulfobetaine surfactants that are suitable for the present invention but do not fall within the scope of the typical structures shown above are N-(3-cocoamidopropyl)-N, N-dimethyl-N-(2-hydroxy-3-sulfopropyl) ammonium betaine and 3-[(3-chloroamidopropyl) dimethylammonium]-1-propane sulfonate.

[0068] In one embodiment, the amphoteric surfactant is an amphoteric surfactant comprising a sulfonic acid. For example, the amphoteric surfactant can be an N-alkyltaurine of the formula RNH-CH2CH2-SO3H, where R is an alkyl group. In a related embodiment, R is an aliphatic group. Another amphoteric surfactant comprising a sulfonic acid can be prepared by sulfonating a linear amidoamine precursor of a 1-hydroxyethyl 2-alkylimidazoline to provide R-CONH-CH2CH2-N(CH2CH2OH)CH2CH2SO3H, where R can be an aliphatic group, for example, an alkyl group.

[0069] Specific examples of amphoteric surfactants and their types that can be used in the compositions of the present invention include, but are not limited to, cocamidopropylamine oxide, cocamidopropyl betaine, cocamidopropyl hydroxysultaine, cocodimethyl sultaine, disodium cocoamphodipropionate, laurylamine oxide, laurylamidopropyl betaine; lauryl betaine, lauryl hydroxysultaine, myristylamine oxide, sodium cocoamphoacetate and stearyl betaine. As previously stated, these terms do not necessarily define mutually exclusive groups of surfactants, i.e., a specific amphoteric surfactant may fall within the scope of two or more groups of amphoteric surfactants that each define one of the selected terms.

[0070] Anionic surfactants

[0071] The fire extinguishing composition of the present disclosure comprises at least one anionic surfactant, and optionally comprises a plurality of anionic surfactants. Suitable exemplary anionic surfactants include, but are not limited to, alkyl sulfates, alkyl ether sulfates, alkyl sulfonates, alkyl aryl sulfonates, alkyl succinates, alkyl sulfosuccinates, N-alkanoyl sarcosinates (alkoylsarcosinates), acyl taurates, acyl isethionates, alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylates, α-olefin sulfonates, and their alkali metal and alkaline earth metal salts and ammonium and triethanolamine salts. Such alkyl ether sulfates, alkyl ether phosphates and alkyl ether carboxylates may contain 1 to 10 ethylene oxide or propylene oxide units per mole, and in some embodiments, 1 to 3 ethylene oxide units per mole. For convenience, anionic surfactants may be represented by reference to the anionic groups forming the charged portion of the surfactant. For example, anionic surfactants comprising sulfonate groups may be referred to as sulfonate surfactants, or, when the context permits, even more simply referred to as sulfonates. As another example, anionic surfactants that contain sulfate groups may be referred to as sulfate surfactants, or even more simply sulfates where the context permits.

[0072] In one embodiment, the anionic surfactant is a carboxylic acid or carboxylate containing an anionic group -C(O)-O- in addition to the aliphatic group. The aliphatic group represented herein as R can be an alkyl group, in which case the carboxylate can be referred to as an alkyl carboxylate. Exemplary alkyl carboxylates are sodium or potassium salts or ammonium salts of fatty acids such as stearic acid and oleic acid. Potassium oleate is an exemplary alkyl carboxylate. Alternatively, the aliphatic group can be a water-insoluble polyoxyalkylene group. Some carboxylate anionic surfactants are prepared from alkyl alcohols, such as octanol, which is then reacted with ethylene oxide to provide a polyoxyethylene extended octanol known as polyoxyethylene (8) octyl ether carboxylic acid when the average number of ethylene oxide units per molecule is 8.

[0073] In one embodiment, the anionic surfactant is diphenyl oxide. Diphenyl oxide can be considered as a subclass of sulfonate anionic surfactants, because the aromatic ring of the diphenyl precursor is sulfonated, so as to provide a diphenyl ether anionic surfactant. The diphenol precursor is usually diphenyl ether, that is, Ar-O-Ar, wherein one or two of the aromatic rings (Ar) can be substituted with an alkyl group. The diphenyl oxide anionic surfactant can be represented by the chemical formula XSO3-Ar(R)-O-Ar(R)-SO3X, wherein R is hydrogen or alkyl at each site of the aromatic ring that is not sulfonated or bonded to the ether oxygen. Exemplary diphenyl oxide anionic surfactants include alkyl-substituted disulfonated diphenyl oxides, such as disulfonated diphenyl oxides substituted by straight-chain decyl groups, disulfonated diphenyl oxides substituted by straight-chain dodecyl groups, and disulfonated diphenyl oxides substituted by branched decyl groups, any of which can be neutralized with sodium, potassium or ammonium.

[0074] In one embodiment, the anionic surfactant is a phosphate ester, that is, it can be a monophosphate ester with a chemical structure of ROP(O)(OH)2, or a phosphoric acid diester with a chemical structure of ROP(O)(OH)-OR, wherein the two Rs in the diester can be the same or different. The R group is an aliphatic group, that is, a water-insoluble group. The R group can be an alkyl group, and the phosphate ester with R=alkyl is usually prepared from the corresponding alkyl alcohol. In one embodiment, the R group is a polyalkylene oxide group to provide a formula R-(OCH2CH2) n -OP(O)(OH)2. The general naming convention for polyether phosphates provides the number of polyoxyethylene groups in the surfactant, for example, polyoxyethylene (10). The R group in the polyether phosphate can be alkyl (when the polyether phosphate is derived from an alkyl alcohol), aryl (when the polyether phosphate is derived from an aromatic alcohol, such as phenol) or alkylaryl, such as an alkyl substituted phenol, such as nonyl-phenol. Exemplary phosphates include polyoxyethylene (10) nonylphenol phosphate, polyoxyethylene (4) phenol phosphate and C8H 17 Phosphate Esters. Commercial preparations of phosphate esters typically provide mixtures of phosphate monoesters and phosphate diesters, which can be used in the compositions of the present disclosure.

[0075] In one embodiment, the anionic surfactant is a sarcosinate, i.e., a compound having the chemical structure RC(O)-N(CH3)-CH2-CO2X, wherein R is an aliphatic group. Sarcosinate surfactants contain an N-acyl group, wherein the fatty acid from which the acyl group is derived is generally used in the nomenclature of the sarcosinate. Exemplary sarcosinates include sodium lauroyl sarcosinate, sodium cocoyl sarcosinate, sodium myristoyl sarcosinate, and ammonium ion equivalents.

[0076] In one embodiment, the anionic surfactant is a sulfate, i.e., a compound containing an anionic -O-SO3X group in addition to an aliphatic group. The aliphatic group can be a long chain alkyl group, wherein the alkyl group in the surfactant can be branched or straight chain. The aliphatic group does not have to be an alkyl group, however, alkyl groups are routinely available from many vegetable and animal oils, so they are a convenient source of aliphatic groups for surfactants. Exemplary sulfate anionic surfactants include sodium laureth sulfate, sodium dodecyl sulfate, sodium decyl sulfate, sodium octyl sulfate, ammonium lauryl sulfate, sodium lauryl sulfate, sodium trideceth sulfate, C 12 – 14 - tert-alkyl-ethoxylated sodium sulfate and poly(oxy-1,2-ethanediyl), α-thio-ω-(nonylphenoxy) ammonium salt.

[0077] In one embodiment, the anionic surfactant is a sulfoacetate, i.e., a compound containing an anionic -CH2-SO3X group in addition to an aliphatic group. Common aliphatic groups have the structure ROC(O)-, where R is an alkyl group, e.g., C8-C 18 Straight chain alkyl. Exemplary sulfoacetate anionic surfactants are sodium lauryl sulfoacetate and hexadecyl ammonium sulfoacetate. Sulfoacetates can be prepared, for example, as described in U.S. Pat. No. 5,616,782.

[0078] In one embodiment, the anionic surfactant is a sulfonate, i.e., a compound containing an anionic -SO3X group in addition to an aliphatic group. The aliphatic group can be, for example, a long chain alkyl group. Sulfonates can be considered to have the chemical structure R-SO3X. In one embodiment, the R group is derived from a fatty acid and is a long straight chain alkyl group, such as stearyl and oleyl. Long chain olefins are often used as precursors for sulfonates because the double bond can be manipulated to convert it to a sulfonate group. Such sulfonates are often named after the precursor used to form the sulfonate, such as C 14 -C 16 Olefin sulfonates, of which C 14 -C 16 The mixture of olefins representing 14 and 16 carbons is a sulfonate providing anionic surfactants. In one embodiment, the R group is an alkylphenyl group, such as a dodecylphenyl group. The alkyl group (e.g., dodecyl) can be a straight chain alkyl group or a branched chain alkyl group. Exemplary sulfonate anionic surfactants are straight chain dodecylbenzene sulfonate and branched chain dodecylbenzene sulfonate. As a rule, any suitable cation can be used to neutralize the anionic group, such as sodium, potassium, ammonium, etc.

[0079] In one embodiment, the anionic surfactant is a sulfosuccinate, i.e., a compound having a chemical structure based on sulfonated succinic acid, i.e., an aliphatic group -OC(O)-CH2-CH(sulfate)-C(O)-OR (which can be an aliphatic group or hydrogen). Sulfosuccinates are typically sodium salts of alkyl esters of sulfosuccinic acid, which are the result of condensation of maleic anhydride with a fatty alcohol followed by sulfonation with sodium bisulfite (NaHSO3). As shown in the aforementioned chemical structure, sulfosuccinates will have at least one aliphatic group and may have two aliphatic groups. However, when sulfosuccinates have one aliphatic group, they may also have an anionic carboxylate group instead of a second aliphatic group. Exemplary sulfosuccinate anionic surfactants include dioctyl sodium sulfosuccinate (having two aliphatic groups) and disodium laureth sulfosuccinate (having one aliphatic group, one sulfate group, and one carboxylate group, and referred to as DLS).

[0080] Other specific examples of the anionic surfactant include, but are not limited to, ammonium lauryl sulfosuccinate, sodium lauryl sulfate, sodium lauryl ether sulfate, ammonium lauryl ether sulfate, triethanolamine dodecylbenzenesulfonate, sodium lauryl sarcosinate, ammonium lauryl sulfate, sodium oleyl succinate, sodium dodecyl sulfate, and sodium dodecylbenzenesulfonate.

[0081] In one embodiment, the fire extinguishing concentrate and composition of the present disclosure include a third surfactant selected from amphoteric surfactants and anionic surfactants. The third surfactant is different from the first (amphoteric) or second (anionic) surfactant, that is, different from the first or second surfactant. Any amphoteric surfactant and anionic surfactant previously disclosed are optionally used as the third surfactant in the formulation of the present invention, as long as it (the third surfactant) is different from the first or second surfactant. In one embodiment, the type of the third surfactant is different from the first or second surfactant, that is, the third surfactant has such a functional group: it is different from the functional group that provides the charged functionality present in the first and second amphoteric surfactants or anionic surfactants. For example, if the second surfactant is a sulfate anionic surfactant, then the third surfactant is not a sulfate, but is, for example, a sulfonate anionic surfactant.

[0082] Suitable amphoteric and / or anionic surfactants for use in the present invention can be obtained from one or more of the following exemplary manufacturers and / or suppliers: Aceto Corp. (Allendale, NJ); Air Products (Allentown, PA); Akzo Nobel Chemicals Co. (Chicago, IL); Alzo International (Sayreville, NJ); BASF Corp. (Florham Park, NJ); Clariant Corp. (Frankfurt, Germany); Croda, Inc. (Edison, NJ); Dow Chemical (Midland MI); EI du Pont deNemours & Co., Inc. (Wilmington, DE); Harcros Chemicals, Inc. (Kansas City, KS); Huntsman Corp. (St. Lake City, UT); Kaiser Industries Ltd. (Bahadurgarh, Haryana, India); Kao Chemicals Ltd. (Kentucky, KY); Chemicals. (Tokyo, Japan); Lonza, Inc. (Basel, Switzerland); NOFCorporation (Tokyo, Japan); Pilot Chemicals (Cincinnati, OH); Procter & Gamble (Cincinnati, OH); Solvay-Rhodia (Courbevoie, France); Stepan Co. (Northfield, IL); and Unilever PLC (London, England).

[0083] Optional components

[0084] The following ingredients are optionally present in the compositions of the present disclosure, however, the present disclosure also provides that each of the following ingredients may be specifically excluded from being present in the compositions of the present disclosure.

[0085] Block copolymers. For example, U.S. Pat. No. 7,915,212 to Yeung et al. is directed to block polymer materials having an average cationic charge density of about 15 or less, preferably 5 or less, measured in units per 100 Daltons of molecular weight at a pH of about 4 to about 12. The polymer materials are disclosed to be effective in fire extinguishing foams.

[0086] The nitrogen-based and phosphorus-nitrogen-based extinguishing materials are selected from the group consisting of melamine cyanurate, melamine orthophosphate, dimelamine orthophosphate, melamine phosphate, melamine borate, melamine octamolybdate, trishydroxyethyl isocyanurate, 2,4-diamino-6-(3,3,3-trichloropropyl)-1,3,5-triazine, 2,4-bis(N-hydroxymethylamino)-6-(3,3,3-trichloropropyl-1,3,5-triazine), dibasic guanidine phosphate, dihydroguanidine phosphate, guanidine carbonate, guanidine sulfamate, urea, urea dihydrogen phosphate, urea ... phosphate), dicyandiamide, bis(2,6,7-trioxa-1-phospha-bicyclo[2,2,2]octane-1-oxy-4-methyl)hydroxyphosphoric acid melamine, 3,9-dihydroxy-3,9-dioxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane-3,9-bismelamine, 1,2-bis(2-oxy-5,5-dimethyl-1,3-dioxa-2-phosphacyclohexyl-2-amino)ethane, N,N'-bis(2-oxy-5,5-dimethyl-1,3-dioxa-2-phosphacyclohexyl)-2,2'-m-phenylenediamine, tris(2-oxy-5,5-dimethyl-1,3-dioxa-2-heterocyclohexyl-2-methyl)amine or chlorophosphazene trimer.

[0087] Phosphorus-halogen based fire extinguishing materials are selected from the group consisting of tris(2,2-dibromomethyl-3-bromopropyl)phosphate, tris(dibromophenyl)phosphate, 3,9-bis(tribromophenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]-3,9-dioxideundecane, 3,9-bis(pentabromophenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]-3,9-dioxideundecane, 1-oxo-4-tribromo Phenyloxycarbonyl-2,6,7-trioxa-1-phosphabicyclo[2,2,2]octane, p-phenylenetetrakis(2,4,6-tribromophenyl)bisphosphate, 2,2-dimethyl-1,3-propanediyl-bis(neopentylglycolato)bisphosphate or 3,9-bis(tribromoneopentyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]-3,9-dioxideundecane.

[0088] The organic phosphorus-based fire extinguishing material is selected from: 1-oxo-4-hydroxymethyl-2,6,7-trioxa-l-phosphabicyclo[2,2,2]octane, 2,2-dimethyl-1,3-propanediyl-di(neopentyl glycol)bisphosphate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 oxide, bis(4-carboxyphenyl)phenylphosphine oxide, bis(4-hydroxyphenyl)phenylphosphine oxide or phenyl phosphate diphenyl sulfone oligomer.

[0089] The chlorine-based fire extinguishing material is selected from the group consisting of dechlorane plus, chlorendic anhydride, perchloropentacyclodecane, tetrachlorobisphenol A, chlorinated polypropylene, chlorinated polyvinyl chloride, vinyl chloride-vinylidene chloride copolymer or chlorinated polyether.

[0090] The bromine-based fire extinguishing material is selected from the group consisting of tetrabromobisphenol A, tetrabromobisphenol A ether, 1,2-bis(tribromophenoxy)ethane, tetrabromophthalic anhydride, N,N-ethylene-bis(tetrabromophthalimide, decabromodiphenyl ether, 1,4-bis(pentabromophenoxy)tetrabromobenzene, 1,2-bis(pentabromophenyl)ethane, bromotrimethylphenylindane, pentabromobenzyl acrylate, hexabromo-benzene, pentabromotoluene, hexabromocyclododecane, N,N'-1,2-ethylene-bis(5,6-dibromonorbomane-2,3-dicarboximide), brominated styrene copolymers, tetrabromobisphenol A carbonate oligomers, polypentabromobenzyl acrylate or polydibromophenylene ether.

[0091] The compositions of the present disclosure may comprise polymer dispersions in the form of water-in-oil emulsions, as disclosed, for example, in European Patent No. 0 774 279 B1. These emulsions comprise a continuous oil phase in which crosslinked, water-swellable polymer particles are dispersed. The polymer particles have a particle size of less than 2 μm, so that they exhibit very rapid swelling times of less than about 3 seconds. Along with their high water absorption capacity, water-in-oil emulsions have the properties of thickeners, so that after mixing with water, a high viscosity fire extinguishing agent or fire retardant is obtained that adheres well to any type of surface, including non-horizontal surfaces.

[0092] As previously described, the compositions of the present disclosure may include a thickener. As used herein, when added to or included in an aqueous fire extinguishing composition or a concentrate thereof, the thickener increases the viscosity of the composition. Among other aspects, the inclusion of a thickener provides improved adhesion of the fire extinguishing composition to a surface. This is particularly advantageous when the surface is non-horizontal, and thus the fire fighting composition will tend to fall from the surface under gravity in the absence of a thickener. The thickener may be water soluble. Thickeners for aqueous compositions are well known in the art and may be referred to as aqueous thickeners, and any such thickener may be used in the compositions of the present invention.

[0093] The amount of thickener included in the composition will depend on the exact characteristics of the thickener and the desired viscosity of the fire extinguishing composition in concentrated form. For thickeners selected from cellulosic materials or polyamide thickeners, and in order to achieve a viscosity similar to that of whole milk or orange juice, when the composition is a concentrate with about 5-25% total solids, the thickener will typically be present in the composition at a weight percentage of 0.1% by weight based on the total weight of the composition. The viscosity of the concentrate can be varied primarily by incorporating more or less thickener. If a more viscous concentrate is desired, adding more thickener will provide a more viscous composition. Alternatively, a more effective thickener may be used, i.e., a thickener that achieves the same viscosity increase at a lower concentration.

[0094] On the one hand, the thickening agent can be a polyhydroxy polymer, for example a polysaccharide such as a cellulosic material or a functionalized cellulosic material. When the thickening agent is a polysaccharide, the polysaccharide can have at least 50, or at least 100, or at least 150, or at least 200 sugar units / polymer chain. The number average molecular weight of the polysaccharide can be at least 13,000, or at least 17,000, or at least 21,000, or at least 25,000.

[0095] In one aspect, the thickener is a small polyhydroxy molecule, such as glycerol. The small polyhydroxy molecule has a molecular weight of less than 500 g / mol and has at least three hydroxyl groups.

[0096] In one aspect, the thickening agent is a cellulosic material, including derivatives of cellulose resins. A suitable cellulosic material is hydroxyethyl cellulose (HEC). HEC is a derivative of cellulose in which the -CH2OH groups are converted to -CH2OCH2CH2OCH2CH2OH groups and the -OH groups are converted to -OCH2CH2OH groups. Many grades of HEC are commercially available, which vary with molecular weight and degree of derivatization, which in turn results in different solution viscosities (typically measured at 2% solids in water). A suitable HEC is Cellosize from Dow Chemical (Midland, MI). TM and Aqualon from Ashland Chemical (Covington, KY). TM .

[0097] Other suitable cellulosic thickeners include methylcellulose, ethylcellulose, methylhydroxyethylcellulose, methylhydroxypropylcellulose, hydroxypropylcellulose and the anionic (salt) forms (eg, sodium carboxymethylcellulose), dihydroxypropyl ethers of cellulose (see, e.g., U.S. Pat. No. 4,096,326).

[0098] In addition to cellulosic materials, suitable polyol polymers include corn starch or modified corn starch, potato starch or modified potato starch, and pectin or modified pectin.

[0099] The thickener can be polyacrylamide. Suitable polyacrylamide thickeners can be selected from copolymers of acrylamide and ammonium acrylate; copolymers of acrylamide or methacrylamide and methacryloxyethyl trimethyl ammonium halide (e.g., chloride); and copolymers of acrylamide and 2-acrylamido-2-methylpropanesulfonic acid. These copolymers can be prepared in the presence of a crosslinking agent, wherein exemplary crosslinking agents include divinylbenzene, tetraallyloxyethane, methylenebisacrylamide, diallyl ether, polyallyl polyglycerol ether, or allyl ethers of alcohols of a sugar series, such as erythritol, pentaerythritol, arabitol, mannitol, sorbitol, and glucose. See, for example, U.S. Patents Nos. 2,798,053 and 2,923,692. Polyacrylamide can be ionic and neutralized with a neutralizer, such as sodium hydroxide, potassium hydroxide, ammonia, or an amine (e.g., triethanolamine or monoethanolamine). Ionic polyacrylamides can be prepared by copolymerization of acrylamide with sodium 2-acrylamido-2-methylpropanesulfonate via a free radical route using an initiator of the azobisisobutyronitrile type and precipitation from an alcohol such as tert-butyl alcohol. Crosslinked copolymers of acrylamide and methacryloyloxyethyltrimethylammonium chloride can be obtained by copolymerization of acrylamide with dimethylaminoethyl methacrylate quaternized with methyl chloride and then crosslinking with compounds containing ethylenically unsaturated groups such as methylenebisacrylamide.

[0100] The thickener may be polyacrylic acid. Suitable polyacrylic acid thickeners are commercially available. For example, Lubrizol (Wickliffe, Ohio) sells its Carbopol 9000, which is made from polyacrylic acid. TM Synthetic thickener. Polyacrylic acid can be neutralized to adjust its thickening properties. For example, polyacrylic acid can be neutralized with ammonium ions, such as ammonium hydroxide. Ashland Chemical sells its Carbomer TM A series of cross-linked polyacrylic acids. Again, these polymers need to be neutralized to provide effective thickening properties.

[0101] Thickeners can be gums or derivatives thereof. Examples include locust bean gum and derivatives, guar gum and derivatives, and xanthan gum and derivatives. Exemplary gum derivatives include sulfonated gums (e.g., sulfonated guar gums), hydroxypropyl-derived gums (e.g., hydroxypropyl guar gums), cationic derivatives (e.g., cationic guar gums).

[0102] Optionally, other polymer stabilizers and thickeners may be incorporated into the concentrate compositions of the present invention to enhance the foam stability of the foam produced by aerating the aqueous solution prepared from the concentrate. Examples of suitable polymer stabilizers and thickeners are: partially hydrolyzed proteins, starches and modified starches, polyacrylic acid and its salts and complexes, polyethylene imine and its salts and complexes, polyethylene resins (e.g., polyvinyl alcohol), polyacrylamides, carboxyvinyl polymers, and poly(oxyethylene) glycols.

[0103] The thickener can be a hydrophobically modified thickener. On the one hand, the thickener comprises a hydrophobic group such as a hydrophobic alkyl chain, wherein suitable examples of such thickeners include hydrophobically modified ethylene oxide urethane (HEUR) polymers, hydrophobically modified alkali-soluble emulsion (HASE) polymers, hydrophobically modified hydroxyethyl cellulose (HMHEC) and hydrophobically modified polyacrylamide (HMPA). The HEUR polymer is a linear reaction product of a diisocyanate and a polyoxyethylene terminated with a hydrophobic hydrocarbon group. The HASE polymer is a homopolymer of (meth) acrylic acid, or a copolymer of (meth) acrylic acid, (meth) acrylate or maleic acid modified with a hydrophobic vinyl monomer. HMHEC refers to hydroxyethyl cellulose modified with a hydrophobic alkyl chain. HMPA refers to a copolymer of acrylamide and acrylamide modified with a hydrophobic alkyl chain (N-alkyl acrylamide).

[0104] As previously mentioned, the compositions of the present disclosure may include inorganic components, optionally including inorganic salts. Inorganic components help cool the flame of combustion: salt water has a greater heat capacity than fresh water. As used herein, the term inorganic component refers to a chemical that does not have a carbon-hydrogen bond. The inorganic component may or may not include metal atoms or ions, but in one embodiment, the composition includes an inorganic material containing a metal, which may be referred to as an inorganic metal component. In different embodiments, the inorganic component has a molecular weight less than 600 g / mol, or less than 400 g / mol, or less than 300 g / mol.

[0105] Suitable inorganic components that do not contain metal atoms or metal ions include ammonium dihydrogen phosphate, ammonium fluoroborate, ammonium hypophosphite, ammonium dihydrogen orthophosphite, ammonium oxalate, ammonium pentaborate, ammonium phosphate, ammonium polyphosphate, ammonium sulfate, ammonium tetraborate hydrate, boron phosphate, diammonium hydrogen phosphate, guanidine nitrate, and guanidine phosphate.

[0106] Suitable inorganic components containing metal atoms or metal ions include basic aluminum oxalate, ammonium aluminum sulfate, aluminum borate whiskers, aluminum dihydrogen phosphate, aluminum hydroxide, ammonium molybdate, aluminum phosphate, potassium aluminum sulfate, aluminum sulfate, ammonium heptamolybdate, ammonium octamolybdate, antimony trioxide, barium metaborate, barium sulfate, basic copper carbonate, basic zinc carbonate, beryllium carbonate, bismuth hydroxide, calcium carbonate, calcium chloride, calcium hydrogen phosphate, cerium hydroxide, cerium carbonate, chromium carbonate, cobalt hydroxide, cobalt carbonate, dimanganese hydrogen phosphate, disodium hydrogen phosphate, dizinc hydrogen phosphate, dolomite (calcium magnesium bicarbonate), dysprosium carbonate, erbium carbonate, europium carbonate, iron hydroxide, ferrocene, ferric acetonate, iron oxide, ferric oxide, ammonium ferrous sulfate, ferrous carbonate, gadolinium carbonate, guanidine carbonate, holmium carbonate, hydrogen phosphate metaborate strontium, hydrogen phosphate potassium ... phosphate strontium metaborate potassium), hydromagnesite, iron nitride, lanthanum carbonate, lanthanum hydroxide, lithium carbonate, lutetium carbonate, magnesium ammonium phosphate, manganese borate, magnesium dihydrogen phosphate, magnesium hydrogen phosphate, magnesium hydrogen sulfate, magnesium hydroxide, magnesium metaborate hydrate, magnesium nitrate, magnesium trisilicate, manganese carbonate, manganese citrate, manganese dihydrogen phosphate, manganese oxalate dihydrate, manganese phosphate, manganese tungstate, manganite, molybdenum hydroxide, monocalcium phosphate, monopotassium phosphate, neodymium carbonate, nickel carbonate, nickel oxalate, potassium bicarbonate, potassium hexafluorotitanate, potassium hexafluorozirconate, potassium metaphosphate, potassium nitrate, potassium oxalate, hexahydrated carbon sodium potassium carbonate, potassium tetraborate hydrate, potassium tripolyphosphate, praseodymium carbonate, samarium carbonate, scandium carbonate, silver carbonate, sodium bicarbonate, sodium citrate, sodium dihydrogen phosphate, sodium nitrate, sodium oxalate, sodium sesquicarbonate, sodium trimetaphosphate, sodium tungstate, strontium carbonate, strontium hydroxide, strontium metaborate, strontium tetraborate, strontium tetraborate hydrate, telluric acid, terbium carbonate, thulium carbonate, tin oxide, titanium dioxide, vanadium carbonate, ytterbium carbonate, yttrium carbonate, zinc oxide, zinc sulfide, zinc sulfate heptahydrate, zinc borate, zinc carbonate, zinc dihydrogen phosphate, zinc phosphate, zinc stannate, zirconium carbonate and zirconium nitrate.

[0107] In one aspect, the fire extinguishing composition of the present disclosure includes an inorganic salt of an organic acid. Suitable inorganic salts of organic acids include ammonium citrate, calcium acetate, copper acetate, copper citrate, magnesium citrate, melamine phosphate, nickel acetate, potassium acetate, potassium citrate, sodium acetate, sodium hydrogen tartrate, strontium acetate, urea phosphate, and zinc acetate.

[0108] The amount of inorganic component present in the composition can change in a wide range.Based on the total weight of the solid present in the composition, inorganic component can constitute 1% to about 15% of this weight.In different embodiments, inorganic component is at least 2% of the total weight of the solid component of the composition, or at least 3%, or at least 4%, or at least 5%, or at least 6%, or at least 7%, or at least 8%, or at least 9%, or at least 10%, or at least 11%, or at least 12%, or at least 13%, or at least 14% or at least 15%.In different embodiments, inorganic component accounts for no more than 30%, or 25%, or 20%, or 15% or no more than 10% of the total weight of the solid present in the composition.As previously mentioned, in one embodiment, inorganic component is an inorganic salt.

[0109] On the one hand, the fire extinguishing concentrate and composition of the present disclosure include a foam generating component or composition, such as AFFF or AR-AFFF, AFFF represents aqueous film-forming foam, and AR-AFFF represents anti-soluble aqueous film-forming foam. Foam generating components or compositions such as AFFF (foam-genetor) will generally include a surfactant, and when the surfactant is one or both of an anionic surfactant and amphoteric surfactant, the foam generator can be used as a medium for introducing anionic surfactants and / or amphoteric surfactants into the concentrate and composition of the present disclosure. Both AFFF and AR-AFFF can be obtained from various commercial suppliers, for example, Kidron Industrial Materials Ltd. (Ramat-Gan, Israel) sells its Dacron AFFF, and Tyco International's Chemguard Company (Mansfield, TX) sells its AFFF products at various solid levels. AFFF and therefore the concentrate and composition of the present disclosure can include a small amount of an organic solvent such as ethylene glycol, for example, trimethyltrimethylene glycol or hexylene glycol. AFFF and thus the concentrates and compositions of the present disclosure may include a fluorinated surfactant. The foam generator may be one of any of U.S. Patent Nos. 5,304,313, 5,464,544, or 5,585,028. AFFF may optionally be identified by U.S. Military Specification MIL-F-24385F.

[0110] In one embodiment, the concentrate of the present disclosure may include small amounts of glycol ethers (ethylene glycol monoethers or ethylene glycol diethers), ethylene glycol, and / or propylene glycol. These materials can be used to extend the life of the foam that can be produced by the concentrate disclosed herein. In one embodiment, ethylene glycol is present in the concentrate at less than 10% of the total weight of the concentrate, or less than 5% of the total weight of the concentrate, and in different embodiments, less than 4%, or less than 3%, or less than 2%, or less than 1%, or less than 0.9%, or less than 0.8%, or less than 0.7%, or less than 0.6% or less than 0.5%, wherein these percentages are weight percentages based on the total weight of the concentrate. For example, the concentrate may include, for example, 1-8 wt% or 2-6 wt% of ethylene glycol monoethers, for example, methyl, propyl, butyl or hexyl monoethers, such as 2-butoxyethanol.

[0111] The composition may include one or more (e.g., all) ingredients selected from the group consisting of: (a) one or more water-soluble polymers selected from the group consisting of xanthan gum, gellan gum, alginate, locust bean gum, derivatized locust bean gum, carrageenan, guar gum, derivatized guar gum, cellulosic materials, succinoglucan, polyacrylamide, starch, and starch derivatives; (b) polyalkylene glycol; and (c) a slurry stabilizer comprising an amine phosphate salt. See U.S. Pat. No. 5,969,012.

[0112] The composition can include a fluorosurfactant, such as an amphoteric fluorosurfactant or an anionic fluorosurfactant. The fluorosurfactant can be a fluorinated or perfluorinated analog of any anionic surfactant or amphoteric surfactant determined above, that is, the fluorinated surfactant used in the concentrate and composition of the present invention can be any anionic surfactant or amphoteric surfactant determined herein, wherein one or more CH bonds in the anionic surfactant or amphoteric surfactant determined herein are replaced with a CF bond. The fluorosurfactant can provide the concentrate and composition of the present disclosure with a desired low surface tension and a positive spreading coefficient that can form a water film on a lighter liquid fuel. Such film formation is desirable because it can contribute to rapid fire extinguishing, anti-sintering and steam release protection.

[0113] As previously described, the present disclosure provides a concentrate composition comprising water and a solid, the solid comprising a first surfactant selected from amphoteric surfactants, a second surfactant selected from anionic surfactants, and a third surfactant selected from amphoteric surfactants and anionic surfactants, the third surfactant being different from the first surfactant and the second surfactant. Optionally, the third surfactant (rather than the first or second surfactant) is a fluorosurfactant. The third surfactant can be a fluorinated or perfluorinated anionic fluorosurfactant, while the second (anionic) surfactant of the concentrate is non-fluorinated. Alternatively, the third surfactant can be a fluorinated or perfluorinated amphoteric surfactant, while the first (amphoteric) surfactant of the concentrate is non-fluorinated. The fluorinated surfactant will contain some CF bonds, and may contain only CF bonds (in which case it is perfluorinated), and may contain some CH bonds (in which case it is a molecule containing hydrofluorocarbons).

[0114] In addition to the fluorinated forms of the amphoteric and anionic surfactants identified herein, other exemplary fluorosurfactants that may be included in the concentrates or compositions of the present disclosure include Captstone TM Fluorosurfactants and Forafac TM Fluorosurfactants, both of which are from DuPont (Wilmington, DE). Other exemplary fluorosurfactants are those disclosed in any of U.S. Patent Publication Nos. US20130112908; US20120255651; US20110232924; US20110091408; US20100168318 and U.S. Patent Nos. US 8,287,752; US 8,039,677; US 7,977,426 and US 7,989,568.

[0115] However, in another embodiment, the third surfactant is not a fluorosurfactant. Fluorinated compounds should be used with caution because they may have undesirable biopersistence characteristics and / or they may decompose into hazardous materials. In one embodiment, the concentrates and compositions of the present invention do not contain any fluorocarbons, while in another embodiment, the concentrates and compositions of the present invention do not contain any halocarbons.

[0116] preparation

[0117] In one embodiment, the present disclosure provides a composition comprising water and a solid, wherein the solid comprises a first amphoteric surfactant, a second anionic surfactant, and a third surfactant selected from amphoteric surfactants and anionic surfactants, wherein the third surfactant is different from the first surfactant and the second surfactant. In an optional embodiment: water accounts for 75wt% to 95wt% of the composition; for example, water accounts for 75wt% to 80wt% of the composition, or water accounts for 80wt% to 85wt% of the composition, or water accounts for 85wt% to 90wt% of the composition, or water accounts for 95wt% to 95wt% of the composition. In an optional embodiment: amphoteric surfactants account for 10wt% to 30wt% of the solid, or account for 15wt% to 25wt% of the solid; for example, amphoteric surfactants account for 10wt% to 15wt% of the solid, or amphoteric surfactants account for 15wt% to 20wt% of the solid, or amphoteric surfactants account for 20wt% to 25wt% of the solid, or amphoteric surfactants account for 25wt% to 30wt% of the solid. In an optional embodiment, amphoteric surfactants account for 1wt% to 5wt% of the composition. In optional embodiments, anionic surfactants account for 45wt% to 85wt% of solids; for example, anionic surfactants account for 45wt%-55wt% of solids, or anionic surfactants account for 55wt%-65wt% of solids, or anionic surfactants account for 65wt%-75wt% of solids, or anionic surfactants account for 75wt%-85wt% of solids. In optional embodiments, anionic surfactants account for 5wt% to 25wt% of the composition.

[0118] In other optional embodiments, the amphoteric surfactant is one or more betaines selected from cocodimethyl sulfopropyl betaine, lauryl betaine and cocamidopropyl betaine; the anionic surfactant is one or more surfactants selected from the following: ammonium lauryl sulfosuccinate, sodium lauryl sulfate, sodium laureth sulfate, sodium lauryl ether sulfate, ammonium lauryl ether sulfate, triethanolamine dodecylbenzenesulfonate, sodium lauryl sarcosinate, ammonium lauryl sulfate, sodium oleyl succinate, sodium dodecyl sulfate, sodium decyl sulfate, sodium octyl sulfate and sodium dodecylbenzenesulfonate; the composition further comprises an inorganic salt, wherein optionally the inorganic salt accounts for 2wt% to 20wt% of the solid; the composition further comprises a thickener, wherein optionally the thickener accounts for 0.1wt% to 5wt% of the solid.

[0119] As previously described, the compositions of the present disclosure contain both amphoteric surfactants (and optionally multiple amphoteric surfactants) and anionic surfactants (and optionally multiple anionic surfactants). In one aspect, the one or more amphoteric surfactants are present in the composition at a weight approximately equal to that of the one or more anionic surfactants. In other aspects, and again measured on a weight basis, the amphoteric surfactants comprise less weight than the anionic surfactants in the total weight of the composition, wherein in various embodiments, the amphoteric surfactants comprise 1% to 50%, or 5% to 40%, or 10% to 30%, or 15% to 25% of the total weight of the anionic surfactants and the amphoteric surfactants.

[0120] When the composition comprises two amphoteric surfactants or two anionic surfactants, the two surfactants are not necessarily present in equal weights. In various embodiments, the composition comprises a first and a second anionic surfactant, wherein the first surfactant provides 1% to 50% of the total weight of the first and second surfactants. In other embodiments, the first surfactant provides 1-40%, or 1%-30%, or 1%-20%, or 1% to 10% or 1% to 5% of the total weight of the first and second anionic surfactants. Similarly, in various embodiments, the composition comprises a first and a second amphoteric surfactant, wherein the first amphoteric surfactant provides 1% to 50% of the total weight of the first and second surfactants, and in other embodiments, the first amphoteric surfactant provides 1%-40%, or 1%-30%, or 1%-20%, or 1% to 10% or 1% to 5% of the total weight of the first and second amphoteric surfactants.

[0121] In one embodiment, a mixture of two amphoteric surfactants is included in the fire extinguishing composition of the present disclosure. For example, any mixture of previously described amphoteric surfactants can be used. When two amphoteric surfactants are present in the composition, the two surfactants will be present in relative amounts based on the weight of each surfactant in the composition. For example, if the composition contains two amphoteric surfactants of equal weight, the two surfactants are present in a weight ratio of 1:1. If the first surfactant contained in the composition is twice the second surfactant, the two surfactants are present in a weight ratio of 1:2. If the second surfactant is present within an allowable weight range relative to the weight of the first surfactant, and the range is "equal to the weight of the first surfactant" to "twice the weight of the first surfactant", the two surfactants are present in a weight ratio of 1:(1-2).

[0122] As described above, in one embodiment, the present disclosure provides for the presence of two amphoteric surfactants in the composition. In various embodiments, the two amphoteric surfactants may be present in any of the following relative amounts: 1:1; 1:(1-5); 1:(1-10); 1:(1-15); 1:(1-20); 1:(1-25); 1:(1-30); 1:(5-10); 1:(5-15); 1:(5-20); 1:(5-25); 1:(5-30); 1:(10-15); 1:(10-20); 1:(10-25); 1:(10-30); 1:(15-20); 1:(15-25); 1:(15-30); 1:(20-25) and 1:(25-30).

[0123] In one embodiment, a mixture of two anionic surfactants is included in the fire extinguishing composition of the present disclosure. For example, any mixture of anionic surfactants previously described can be used. When two anionic surfactants are present in the composition, the two surfactants will be present in relative amounts based on the weight of each surfactant in the composition. For example, if the composition contains two anionic surfactants of equal weight, the two surfactants are present in a weight ratio of 1:1. If the first surfactant contained in the composition is twice the second surfactant, the two surfactants are present in a weight ratio of 1:2. If the second surfactant is present within an allowable weight range relative to the weight of the first surfactant, and the range is "equal to the weight of the first surfactant" to "twice the weight of the first surfactant", the two surfactants are present in a weight ratio of 1:(1-2).

[0124] As described above, in one embodiment, the present disclosure provides the presence of two anionic surfactants in the composition. In various embodiments, the two anionic surfactants may be present in any of the following relative amounts: 1:1; 1:(1-5); 1:(1-10); 1:(1-15); 1:(1-20); 1:(1-25); 1:(1-30); 1:(5-10); 1:(5-15); 1:(5-20); 1:(5-25); 1:(5-30); 1:(10-15); 1:(10-20); 1:(10-25); 1:(10-30); 1:(15-20); 1:(15-25); 1:(15-30); 1:(20-25) and 1:(25-30).

[0125] In one embodiment, the present disclosure provides a fire extinguishing concentrate composition, the fire extinguishing concentrate composition comprising 10-25 wt% of a first anionic surfactant, optionally a sulfonate surfactant such as sodium dodecylbenzene sulfonate, optionally 12-23 wt% or optionally 15-20 wt% of a first anionic surfactant; 5-15 wt% of an amphoteric surfactant, optionally a betaine surfactant such as cocamidopropyl betaine, optionally 7-13 wt% or optionally 7-11 wt% of a betaine surfactant; 1-10 wt% of a second anionic surfactant, Optionally a sulfate surfactant such as sodium laureth sulfate or sodium dodecyl sulfate, optionally 2-8 wt% or 3-7 wt% of a second anionic surfactant; up to about 5 wt% of an organic solvent, optionally a glycol ether such as butyl glycol, optionally 1-4 wt% or 2-3 wt% of glycol ether; 2-15 wt% of a thickener such as a cellulosic thickener, for example hydroxyethyl cellulose, optionally 4-12 wt% or 6-10 wt% of a thickener; up to about 10 wt% of calcium chloride, optionally 2-7 wt% or 3-6 wt% of calcium chloride. Optionally, the concentrate may contain a third anionic surfactant such as sodium octyl sulfate in an amount up to about 5 wt%. Water will also be present in the concentrate. The total non-water content of the concentrate is about 25-75 wt%, or about 30-70 wt%, or about 35-55 wt%, or about 40-50 wt% (in the last case, the water content is 50-40 wt%).

[0126] Manufacturing method

[0127] In one aspect, the present disclosure provides methods for preparing fire extinguishing concentrate compositions and corresponding fire extinguishing compositions as defined herein. Typically, the concentrate is prepared by combining water with at least three different surfactants selected from anionic surfactants and amphoteric surfactants and optional ingredients. The composition is prepared by diluting the concentrate with water or an aqueous solution.

[0128] In one embodiment, the concentrate is prepared by combining a first surfactant that is an amphoteric surfactant, a second surfactant that is an anionic surfactant, and a third surfactant selected from an amphoteric surfactant and an anionic surfactant, wherein the third surfactant is different from the first or second surfactant. The concentrate may optionally contain other surfactants, i.e., a fourth, fifth, etc. surfactant. In addition, or alternatively, the concentrate may contain active ingredients, such as inorganic components, organic solvents, and thickeners, in addition to the surfactants. The compositions are water-based, in other words, they are aqueous compositions because the carrier is primarily water. The compositions may be prepared by any of the following methods.

[0129] In one embodiment, a container for holding water is provided. Such a container holds about 5 kg to 20 kg of water. Of course, the method can be scaled up or down to provide a desired amount of fire extinguishing concentrate. The initial amount of water is about 5-40%, or about 10-30%, of the total amount of water in the concentrate. The water can be at ambient temperature or it can be at an elevated temperature. An elevated temperature below the boiling point of water can be used, i.e., below 100° C., or below 90° C., or below 80° C., or below 70° C. An elevated temperature exceeding ambient temperature can be used, for example, above 25° C., or above 30° C., or above 40° C., or above 50° C., or above 60° C., or above 70° C.

[0130] The surfactant is then added to the water. In one embodiment, the amphoteric surfactant is added to the water, followed by the sequential addition of the first and second anionic surfactants. In an alternative embodiment, the anionic surfactant is first added to the water, followed by the amphoteric surfactant, followed by the second anionic surfactant or the second amphoteric surfactant. In another embodiment, the first and second anionic surfactants are sequentially added, followed by the addition of the amphoteric surfactant.

[0131] After the surfactant is added to the water, the resulting mixture is stirred to provide a uniform or nearly uniform state. Stirring can be performed slowly or violently, but, in either case, preferably no excessive foam is produced. Foam is usually caused by trapped air in the mixture, wherein when significant eddy currents are generated during the mixing process and / or when the stirring device repeatedly enters and exits the mixture, the air tends to be trapped. When the viscosity of the mixture is large, the foam retention also tends to be stronger. These situations are preferably avoided to minimize the foam generation. In order to ensure good mixing, after adding each surfactant, a stirring time of about 15-60 minutes can be adopted.

[0132] Depending on the presence or absence of insulation around the container in which the concentrate is prepared, the temperature of the mixture may drop during the surfactant addition and agitation steps. Alternatively, the temperature of the mixture may be maintained at or near the original temperature of the water by, for example, maintaining slight heat to the sides and / or bottom of the container holding the concentrate. Alternatively or in addition, a heating coil may be placed within the container to add or recover heat from the concentrate as desired.

[0133] As a result of adding surfactants to the water, the viscosity of the mixture will tend to increase. All other factors being equal, solutions of increased viscosity will tend to entrap air more easily than solutions of lower viscosity. To reduce the viscosity of the mixture, additional water may be added to the mixture after any of the first, second, or third surfactants are added. For example, an amount of water of about 5-40% or about 10-30% of the total amount of water in the concentrate may be added to the mixture after the first addition of the surfactant. Additionally or alternatively, an amount of water of about 5-40% or about 10-30% of the total amount of water in the concentrate may be added to the mixture after the second addition of the surfactant.

[0134] After all additives have been added and fully mixed into the water, optional ingredients may be added to the resulting mixture. For example, inorganic components such as inorganic salts may be added to the mixture and then stirred to fully dissolve the inorganic components. Optional ingredients may be added to the warm or hot mixture, or added to the mixture after it has cooled to room temperature. Since concentrates are typically stored and used at room temperature, any optional ingredients that significantly affect the viscosity or flow characteristics of the mixture are typically added to the mixture at room temperature.

[0135] The surfactants and optional ingredients can be added to the water in pure form (i.e., not in contact with a solvent), or in diluted form (i.e., in contact with a solvent) to provide a solution, paste, dispersion, etc. of the ingredients. In one embodiment, the surfactants are added to the water in the order of their solids content in the water, with the more concentrated ingredients being added first. In other words, if a surfactant is 50% solids and another surfactant is 25% solids, the surfactant at 50% solids is added to the water before the surfactant at 25% solids is added to the mixture.

[0136] Concentrates can be prepared in intermittent, continuous or semi-continuous modes. In intermittent mode, ingredients are sequentially added to a container filled with water until all ingredients have been added, in which case a batch of concentrates has been prepared. In continuous mode, water is driven forward by a pipe or other conduit, and each ingredient is added to the water at different points along the conduit. For example, the conduit can be equipped with a T-valve, wherein the ingredients can be sent to water or an aqueous mixture by the T-valve. The conduit can also include a mixer (static mixer or pipeline mixer) in the conduit to promote the production of a uniform mixture after the ingredients are added to the water or aqueous mixture. For example, water and the first surfactant can be sent to the pipe and passed through the mixer. Generally, if the surfactant is dissolved in water in advance, a static mixer is sufficient. Otherwise, a pipeline mixer is generally preferred. Thereafter, the second surfactant is added to the conduit downstream of the mixer, which is once again subjected to a mixing process. Finally, the third surfactant is added to the aqueous mixture, and then mixed as needed to provide an aqueous mixture comprising three surfactants. Thereafter, other optional ingredients may be added to the conduit through, for example, a T-valve, followed by appropriate stirring to form the final concentrate.

[0137] In order to promote mixing of the different ingredients and to minimize vortex formation and thus foam formation, baffles may be installed in batch or continuous reactors. Suitable mixing equipment (e.g., agitators, impellers, static mixers, colloid mills and homogenizers) are manufactured and sold by, for example, Chemineer (Dayton, Ohio) and Sulzer (Winterthur, Switzerland).

[0138] In an alternative embodiment of the continuous process, three T-valves are located at the beginning of the conduit, at a position after water is added to the conduit. The first, second and third surfactants are delivered into the conduit through one of the three T-valves. In this way, the three surfactants are combined substantially simultaneously, and then the resulting mixture is passed through an in-line mixer or a static mixer in the conduit to provide a uniform aqueous mixture. The optional ingredients are then added to the uniform aqueous mixture as needed to provide a final concentrate.

[0139] In a continuous or batch process, the water and / or aqueous mixture may be heated to a temperature above ambient temperature, for example, a temperature of 50° C. to 90° C. The heating may be accomplished by conventional methods known in the art. The elevated temperature may be maintained as needed to promote rapid mixing of the ingredients to form a homogeneous mixture.

[0140] Therefore, in one embodiment, the present disclosure provides a continuous method for preparing a fire extinguishing concentrate composition. The method comprises: providing a continuous reactor, injecting water into the continuous reactor, adding a) a first anionic surfactant, b) a second amphoteric surfactant, and c) a third surfactant selected from anionic surfactants and cationic surfactants to the water in the continuous reactor, wherein the third surfactant is different from the first surfactant and the second surfactant; and mixing components a), b) and c) to provide a uniform mixture. Optionally, the continuous reactor is maintained at a temperature exceeding 50°C. Also optionally, a mixer selected from a pipeline mixer and a static mixer is present in the continuous reactor.

[0141] How to use

[0142] The present disclosure provides a fire extinguishing concentrate that can be used in a fire extinguishing process. In one embodiment, the fire extinguishing concentrate is diluted with water to provide a fire extinguishing composition that is directly applied to the fire. The concentrate will have a solid level or content measured as the total weight of the non-water components in the concentrate divided by the total weight of the concentrate. When water is combined with the concentrate to form a fire extinguishing composition, the fire extinguishing composition will also have a solid level or content that will be lower than the solid level or content of the concentrate. In various embodiments, the composition is formed by combining sufficient water with the concentrate to provide a fire extinguishing composition having the following solid weight percentage based on the total weight of the composition: 0.1%, or 0.5%, or 1%, or 1.5%, or 2%, or 2.5%, or 3%, or 3.5%, or 4%, or 4.5%, or 5%, or 5.5%, or 6%, or 6,5%, or 7%, or 7.5%, or 8%, or 8.5%, or 9%, or 9. 5%, or 10%, or 10.5%, or 11%, or 11.5%, or 12%, or 12.5%, or 13%, or 13.5%, or 14%, or 14.5%, or 15%, or 15.5%, or 16%, or 16.5%, or 17%, or 17.5%, or 18%, or 18.5%, or 19%, or 20%, or a concentration within the range provided by any two of the above solid percentage values, for example, 0.5% to 4%.

[0143] On the one hand, the preparation personnel will obtain the supply of the stored fire extinguishing concentrate, which can be easily obtained when fire extinguishing is needed, and the method of combining the concentrate with water can be obtained to form a fire fighting composition. In one embodiment, the dilution process utilizes the Venturi effect, which is observed when a fluid (such as water) flows through a narrowed pipe, thereby providing a partial restriction with a diameter narrower and smaller than a large volume pipe. In this case, the partial restriction causes an increase in the pressure in the pipe, and the pressure difference causes the fluid to accelerate to flow to the narrow part of the low pressure, so the fluid maintains a higher speed therein. When pure water flows through the pipe and the pipe is in fluid communication with the reservoir of the fire extinguishing concentrate of the present disclosure, this pressure change (Venturi effect) can be used to extract the concentrate from the reservoir and allow it to enter the pure water, thereby diluting the concentrate and forming a fire extinguishing composition.

[0144] This venturi effect can be used to prepare the fire extinguishing composition of the present disclosure. For example, an aircraft flying over a fire can carry a container containing water and a container containing a concentrate. A nozzle is directed toward the fire, wherein the nozzle is connected to a tube that is in fluid communication with the pure water and the concentrate of the present disclosure. As the water is pumped out of the reservoir and through the nozzle, a venturi effect can be established that will draw the concentrate from the reservoir and into the water. The water and concentrate will mix in the nozzle to provide the fire extinguishing composition of the present disclosure, which is then directed from the aircraft onto the fire.

[0145] In a related aspect, and on a very small scale, a container of fire extinguishing concentrate can be placed under a sink in a home. The container is secured to a tube that can be connected to the faucet of the sink when a fire occurs. When the faucet is turned on, a venturi effect can be created that draws the concentrate into the tube. The tube will have a nozzle that can be pointed at the fire. In this way, a fire extinguishing composition can be formed in a home and used to extinguish dangerous fires.

[0146] The fire extinguishing concentrate as disclosed herein can be diluted with water to produce a fire extinguishing composition. The dilution process can optionally involve any fixed or portable in-line injector, in-line balanced pressure and pump pressure proportioning ski, air tank balanced pressure proportioning system, ratio regulator around the pump, or hand-held hose (handline) air suction nozzle with fixed injector suction pipe. The fire extinguishing composition can be optionally discharged onto the fire by using any of the following: foam chamber, air suction or non-air suction nozzle or nozzle, standard water mist nozzle for hand-held hose and monitor, air suction foam nozzle, foam generator used with floating roof tank of Dike / Bund protection system or high back pressure foam made for subsurface bottom injection system.

[0147] Methods that can be used to store and / or deliver the fire extinguishing concentrates and compositions of the present disclosure can be found in, for example, U.S. patents and patent application numbers US8,646,540; US8,505,642; US8,459,369; US8,453,751; US8,439,123; US8,087,468; US8,042,619; US7,905,296; US7,823,650; US5762145; US20130211173; US20130025888 and US20120199370.

[0148] Fire extinguishing concentrate and composition of the present disclosure can be used to extinguish various types of flames. For example, concentrate and composition of the present disclosure can be used to resist hydrocarbon fires, such as fires in which hydrocarbons are gasoline, oil, diesel, fuel oil, heptane, hexane or cyclohexane. As another example, fire fighting concentrate and composition of the present disclosure can be used to resist polar liquid fires, such as fires in which polar liquids are alcohols (e.g., methanol, ethanol and isopropanol), ketones (e.g., dimethyl ketone and methyl isobutyl ketone), esters (e.g., n-butyl acetate) and ethers (e.g., methyl tert-butyl ether). As another example, concentrate and composition of the present disclosure can be used to resist Class A fires, which are fires fueled by burning materials that leave ash residues (e.g., paper, wood, cloth, rubber and some plastics).

[0149] The following examples are provided to illustrate embodiments of the present disclosure and should not be construed as limiting the embodiments of the present disclosure.

[0150] Example

[0151] In the following examples, the commercial products shown may not have the indicated solids content or neutralization as used in the examples. In such cases, the commercial products may be diluted with water to the indicated solids content and / or neutralized with an acid or base as needed to provide the indicated neutralized form. Thickeners are added to provide a final viscosity close to that of whole milk or orange juice.

[0152] Example 1

[0153] To about 10 kg of hot water (about 75° C.) are added the following ingredients in sequence, stirring for about 30 minutes after each addition in a manner to minimize foam formation: a first anionic surfactant solution (about 9 kg of sodium branched dodecylbenzene sulfonate (about 60% solids) in water, such as SULFONIC 100 from Stepan Company, after neutralization with sodium hydroxide), an amphoteric surfactant solution (about 4.5 kg of cocamidopropyl betaine (about 35% solids) in water, such as AMPHOSOL CA from Stepan Company), hot water (about 9 kg), a second anionic surfactant solution (about 11 kg of sodium lauryl ether sulfate (about 3% solids) in water, such as CALFOAM ES-703 from Pilot Chemical Co.), and an inorganic salt solution (about 2 kg of calcium chloride (about 30% solids) in water, wherein the calcium chloride is available in both solid and solution form, for example, from OxyChem, Ludington, MI). The resulting mixture is allowed to cool to ambient temperature (about 8 hours) before adding a thickener (about 4 kg sodium carboxymethylcellulose (about 1.5% solids) in water, such as AQUALON, Ashland Chemicals, Covington, KY) to provide a final fire extinguishing concentrate.

[0154] Example 2

[0155] To about 10 kg of hot water (about 75° C.) are added the following ingredients in sequence, with stirring for about 30 minutes after each addition in a manner to minimize foam formation: a first anionic surfactant solution (about 9 kg triethanolamine dodecylbenzenesulfonate (about 53% solids) in water, CALSOFT T60 (Pilot Chemical)), an amphoteric surfactant solution (about 4.5 kg aqueous solution of sodium cocoamphoacetate (about 35% solids) in water, AMPHITOL 20Y-B (Kao Chemicals)), hot water (about 6.5 kg), a second anionic surfactant solution (about 14 kg ammonium lauryl sulfate (about 7% solids) in water, EMALAD-25R (Kao Chemicals)), and an inorganic salt solution (about 2 kg calcium chloride (about 30% solids) in water, wherein the calcium chloride is available in both solid and solution form, for example, from OxyChem, Ludington, MI). The resulting mixture is allowed to cool to ambient temperature (about 8 hours) before adding a thickener (about 4 kg sodium carboxymethylcellulose (about 1.5% solids) in water, such as WALOCEL CRT, Dow Chemical) to provide a final fire extinguishing concentrate.

[0156] Example 3

[0157] To about 8 kg of hot water (about 75° C.) are added the following ingredients in sequence, with stirring for about 30 minutes after each addition in a manner to minimize foam formation: a first anionic surfactant solution (about 8.5 kg of sodium lauryl sulfoacetate (about 53% solids) in water, LATHANOL LAL flake (Stepan Co.)), an amphoteric surfactant solution (about 6.3 kg of lauryl hydroxysulfobetaine (about 30% solids) in water, AMPHITOL 20HD, Kao Chemicals), hot water (about 6.5 kg), a second anionic surfactant solution (about 14 kg of sodium octyl phenol ethoxylate sulfate (about 7% solids) in water, POE-3, POLY-STEP C-OP3S (Stepan Co.)), and an inorganic salt solution (about 2 kg of an aqueous solution of calcium chloride (about 30% solids) in water, wherein the calcium chloride is available in both solid and solution form, for example, from OxyChem, Ludington, MI). The resulting mixture is allowed to cool to ambient temperature (about 8 hours) before adding a thickener (about 4 kg sodium carboxymethylcellulose (about 1.5% solids) in water, such as AQUALON, Ashland Chemicals, Covington, KY) to provide a final fire extinguishing concentrate.

[0158] Example 4

[0159] To about 8.5 kg of hot water (about 75° C.) are added the following ingredients in sequence, with stirring for about 30 minutes after each addition in a manner to minimize foam formation: a first anionic surfactant solution (about 9 kg of polyoxyethylene (10) nonylphenol phosphate (about 53% solids) in water, FOSFODET 9Q / 22 (Kao Chemicals)), an amphoteric surfactant solution (about 5.3 kg of disodium cocoamphodipropionate (about 35% solids) in water, CRODATERIC CADP 38 (Croda)), hot water (about 6 kg), a second anionic surfactant solution (about 14 kg of sodium dioctylsulfosuccinate (about 7% solids) in water, STEPWET DOS-70 (Stepan Co.)), and an inorganic salt solution (about 3.3 kg of calcium chloride (about 30% solids) in water, wherein the calcium chloride is available in both solid and solution form, for example, from OxyChem, Ludington, MI). The resulting mixture is allowed to cool to ambient temperature (about 8 hours) before adding a thickener (about 4 kg sodium carboxymethylcellulose (about 1.5% solids) in water, such as WALOCEL CRT, Dow Chemical) to provide a final fire extinguishing concentrate.

[0160] Example 5

[0161] To about 15 kg of hot water (about 75° C.) are added the following ingredients in sequence, with stirring for about 30 minutes after each addition in a manner to minimize foam formation: a first anionic surfactant solution (about 5 kg of polyoxyethylene (8) caprylyl ether carboxylic acid (about 53% solids) in water, AKYPO LF2 (Kao Chemical)), an amphoteric surfactant solution (about 8.3 kg of cocamidopropylamine oxide (about 30% solids) in water, CALOXAMINE CPO (Pilot Chemical)), hot water (about 14 kg), a second anionic surfactant solution (about 7.5 kg of sodium lauroyl sarcosinate (about 20% solids) in water, MAPROSYL 30-B (Stepan Co.)), and an inorganic salt solution (about 3.3 kg of calcium chloride (about 30% solids) in water, wherein the calcium chloride in both solid and solution form is available from, for example, OxyChem, Ludington, MI). The resulting mixture is allowed to cool to ambient temperature (about 8 hours) before adding a thickener (about 4 kg sodium carboxymethylcellulose (about 1.5% solids) in water, such as AQUALON, Ashland Chemicals, Covington, KY) to provide a final fire extinguishing concentrate.

[0162] Example 6

[0163] To about 14 kg of hot water (about 75° C.) are added the following ingredients in sequence, with stirring for about 30 minutes after each addition in a manner to minimize foam formation: a first anionic surfactant solution (about 5.6 kg potassium oleate (about 50% solids) in water, ICTEOL K-50 (Kao Chemicals)), an amphoteric surfactant solution (about 8.3 kg cocamidopropyl betaine (about 30% solids) in water, CALTAINE C-35 (Pilot Chemical)), hot water (about 15 kg), a second anionic surfactant solution (about 6 kg linear decyl substituted bissulfonated diphenyl oxide (about 20% solids) in water, DOWFAX C10L, (Dow Chemical)), and an inorganic salt solution (about 3.3 kg calcium chloride (about 30% solids) in water, wherein the calcium chloride is available in both solid and solution form, for example, from OxyChem, Ludington, MI). The resulting mixture is allowed to cool to ambient temperature (about 8 hours) before adding a thickener (about 4 kg sodium carboxymethylcellulose (about 1.5% solids) in water, such as WALOCEL CRT, Dow Chemical) to provide a final fire extinguishing concentrate.

[0164] Example 7

[0165] To about 15 kg of hot water (about 75° C.) are added the following ingredients in sequence, with stirring for about 30 minutes after each addition in a manner to minimize foam formation: a first anionic surfactant solution (about 5 kg of isopropylamine dodecylbenzenesulfonate (about 50% solids) in water, NINATE 411 (Stepan Co.)), an amphoteric surfactant solution (about 10 kg of cocamidopropyl hydroxysultaine (about 30% solids) in water, AMPHOSOL CS-50 (Stepan)), hot water (about 15 kg), a second anionic surfactant solution (about 5 kg of sodium dodecylbenzenesulfonate (about 30% solids) in water, MELIOSOL 50X (Kao Chemical)), and an inorganic salt solution (about 3.3 kg of calcium chloride (about 30% solids) in water, wherein the calcium chloride is available in both solid and solution form, for example, from OxyChem, Ludington, MI). The resulting mixture is allowed to cool to ambient temperature (about 8 hours) before adding a thickener (about 4 kg sodium carboxymethylcellulose (about 1.5% solids) in water, such as AQUALON, Ashland Chemicals, Covington, KY) to provide a final fire extinguishing concentrate.

[0166] Example 8

[0167] To about 20 kg of hot water (about 75° C.) are added the following ingredients in sequence, with stirring for about 30 minutes after each addition in a manner to minimize foam formation: a first anionic surfactant solution (about 8.4 kg alkyl-substituted bissulfonated diphenyl oxide in water (about 50% solids), DOWFAX C10L (Dow Chemical)), an amphoteric surfactant solution (about 6.7 kg lauramidopropyl betaine in water (about 30% solids), AMPHITOL 20AB (Kao Chemicals)), hot water (about 12 kg), a second anionic surfactant solution (about 4 kg sodium C14-C16 olefin sulfonate in water (about 20% solids), ALFANOX 46 (Kao Chemical)), and an inorganic salt solution (about 1.7 kg calcium chloride in water (about 30% solids), wherein the calcium chloride in both solid and solution form is available from, for example, OxyChem, Ludington, MI). The resulting mixture is allowed to cool to ambient temperature (about 8 hours) before adding a thickener (about 4 kg sodium carboxymethylcellulose (about 1.5% solids) in water, such as WALOCEL CRT, Dow Chemical) to provide a final fire extinguishing concentrate.

[0168] Example 9

[0169] To about 10 kg of hot water (about 75° C.) are added the following ingredients in sequence, stirring for about 30 minutes after each addition in a manner to minimize foam formation: a first anionic surfactant solution (about 9 kg of sodium linear dodecylbenzene sulfonate (about 60% solids) in water, such as CALSOFT F90 (Pilot Chemical)), an amphoteric surfactant solution (about 4.5 kg of cocamidopropyl betaine (about 35% solids) in water, such as AMPHOSOL CA from Stepan Company), hot water (about 9 kg), a second anionic surfactant solution (about 11 kg of sodium lauryl ether sulfate (about 3% solids) in water, such as CALFOAM ES-703 from Pilot Chemical Co.), and an inorganic salt solution (about 2 kg of calcium chloride (about 30% solids) in water, wherein the calcium chloride is available in both solid and solution form, for example, from OxyChem, Ludington, MI). The resulting mixture is allowed to cool to ambient temperature (about 8 hours) before adding a thickener (about 4 kg sodium carboxymethylcellulose (about 1.5% solids) in water, such as AQUALON, Ashland Chemicals, Covington, KY) to provide a final fire extinguishing concentrate.

[0170] Example 10

[0171] To about 10 kg of hot water (about 75° C.) are added the following ingredients in sequence, stirring for about 30 minutes after each addition in a manner to minimize foam formation: a first anionic surfactant solution (about 9 kg of sodium linear dodecylbenzene sulfonate in water (about 60% solids), such as CALSOFT F90 (Pilot Chemical)), an amphoteric surfactant solution (about 4.5 kg of cocamidopropyl betaine in water (about 35% solids), such as AMPHOSOL CA from Stepan Company), hot water containing dissolved butyl glycol ether (about 9 kg of water and about 1 kg of ether), a second anionic surfactant solution (about 11 kg of sodium laureth sulfate in water (about 3% solids), such as CALFOAM ES-703 from Pilot Chemical Co.), and an inorganic salt solution (about 2 kg of calcium chloride in water (about 30% solids), wherein the calcium chloride is available in both solid and solution form, for example, from OxyChem, Ludington, MI). The resulting mixture is allowed to cool to ambient temperature (about 8 hours) before adding a thickener (about 4 kg sodium carboxymethylcellulose (about 1.5% solids) in water, such as AQUALON, Ashland Chemicals, Covington, KY) to provide a final fire extinguishing concentrate.

[0172] The effectiveness of the fire extinguishing concentrates and compositions of the present disclosure can be evaluated by one or more test methods that indicate the fire extinguishing effectiveness of the composition. The following are exemplary test methods that can be employed.

[0173] The test flame was prepared using a 19.5" x 19.5" pan filled with 1" of water and 1" of diesel with a splash of heptane. The nozzle was placed directly above the pan at a height of 37.5" above the bottom of the pan. The release cylinder was filled with 1L of 3.5% solids fire extinguishing composition and pressurized to 250PSI with nitrogen. Ignite, and after a 2 min pre-burn, release the composition. The time for the flame to be completely extinguished was measured.

[0174] A test flame of 28 ft2 in size is produced in a horizontal circular dish of 6 feet in diameter, made of 0.25-inch (0.25-in.) thick steel with 4-foot (4-in.) high sides. A shallow layer of water is used to protect the bottom of the dish and to ensure that the fuel completely covers the area. A nozzle is used to deliver the composition to the flame, for example, a nozzle for foam application is a 2 gal / min nozzle. 10 gallons of unleaded gasoline fuel that meets ASTM D439 is poured in a 30-sec time, ignited within 30 sec of refueling, and allowed to burn freely for 10 sec. After the pre-combustion period, the flame is fought and extinguished as quickly as possible. The time for the flame to be completely extinguished is measured.

[0175] The flame is prepared by fixing the tire to the test structure and then applying a 50 / 50 mixture of kerosene and diesel fuel directly to the tire before ignition. After the test begins, a flame accelerant is optionally applied to the tire to increase the combustion of the tire. After the tire is allowed to burn for a sufficient time to ensure that the rubber is on fire and the flame is not only derived from the combustion of the flame accelerant, the composition of the present disclosure is directed to the burning tire. The time to extinguish all visible flames is measured. For example, a tire and about 1 kg of foam plastic are ignited. The foam plastic is basically used as a fire starter: it is easy to ignite and burns continuously near the tire, thereby heating and eventually igniting the tire. After the tire begins to burn, two hundred milliliters of diesel are added to increase the fire. Once the flame reaches about 750-850°C, different flame retardants are tried to extinguish the fire. In one example, successive cans of 3kg ABC dry chemical fire extinguisher are applied to the fire. Although each application of dry chemical fire extinguisher can slowly or seem to temporarily extinguish the flame, they are ineffective in permanently extinguishing the flame, even after consuming three cans, the flame can resume its complete flame. In contrast, a 400cc aerosol bottle of a fire extinguisher composition according to the present disclosure (e.g., as disclosed in Examples 1-10) is applied to a single burning tire (prepared as described above). The fire can be easily extinguished by applying about 2 / 3 of the 400cc bottle. After a minute or so, the flames may resume, while the remaining 1 / 3 of the 400cc bottle of fire extinguisher composition can be permanently extinguished. After being extinguished by such a composition, the approximate temperature of the fire is 55°C to 65°C. Thus, the fire extinguisher composition of the present disclosure shows a more effective ability to extinguish the flames of burning tires than a standard ABC type fire extinguisher composition.

[0176] The test flame was prepared using a 1 / 4" x 24" x 36" gauge steel plate with a drain hole on one end of the plate. A 1 / 4" x 2" 90° edge was welded around the perimeter of the plate to contain excess splatter. Five (5) grams of magnesium were placed in a pile on the steel plate approximately 6" from each side of one corner. The magnesium was ignited and allowed to burn for approximately seven (7) seconds. At this point, a composition of the present disclosure was applied to the fire using a one quart spray bottle filled with the composition. The extinction time and flame size of the magnesium flame was recorded.

[0177] The test flame was prepared by placing 1 liter of salad oil in a pan with a radius of 30 cm and heating the oil to about 400° C., whereupon it burned. A 500 mL portion of the fire extinguishing composition of the present disclosure was sprayed on the flame. The time for the flame to extinguish was measured.

[0178] The present disclosure includes the following numbered embodiments, which are merely exemplary and do not limit the various embodiments of the present disclosure:

[0179] 1. A composition comprising water and dissolved or suspended solids, the solids comprising a first surfactant selected from amphoteric surfactants and a second surfactant selected from anionic surfactants.

[0180] 2. The composition according to embodiment 1, wherein the first surfactant is a betaine surfactant, or in other words, a surfactant comprising a betaine group.

[0181] 3. The composition of embodiment 1, wherein the first surfactant is amidopropyl betaine.

[0182] 4. The composition of embodiment 3, wherein the amidopropyl betaine is cocamidopropyl betaine.

[0183] 5. The composition of embodiment 3, wherein the amidopropyl betaine is isostearyl propyl betaine.

[0184] 6. The composition of embodiment 3, wherein the amidopropyl betaine is lauroamidopropyl betaine.

[0185] 7. The composition of embodiment 1, wherein the first surfactant is an amphoteric acetate surfactant.

[0186] 8. The composition of embodiment 7, wherein the amphoacetate is sodium cocoamphoacetate.

[0187] 9. The composition of embodiment 7, wherein the amphoacetate is sodium lauroamphoacetate.

[0188] 10. The composition of embodiment 1, wherein the first surfactant is an amphoteric propionate surfactant.

[0189] 11. The composition of embodiment 10, wherein the amphoteric propionate is disodium cocoamphodipropionate.

[0190] 12. A composition as described in embodiment 10, wherein the amphoteric propionate is sodium capryloylamphopropionic acid.

[0191] 13. The composition of embodiment 1, wherein the first surfactant is a hydroxysulfobetaine surfactant.

[0192] 14. The composition of embodiment 13, wherein the hydroxysultaine is cocamidopropyl hydroxysultaine.

[0193] 15. The composition of embodiment 13, wherein the hydroxysultaine is oleamidopropyl hydroxysultaine.

[0194] 16. The composition of embodiment 13, wherein the hydroxysultaine is lauryl hydroxysultaine.

[0195] 17. The composition of embodiment 1, wherein the first surfactant is an amine oxide surfactant.

[0196] 18. The composition of embodiment 17, wherein the amine oxide is cocamidopropylamine oxide.

[0197] 19. A composition as described in embodiment 17, wherein the amine oxide is N,N-(dihydroxyethyl)myristylamine oxide.

[0198] 20. The composition of embodiment 1, wherein the first surfactant is an imidazoline derivative.

[0199] 21. The composition of embodiment 20, wherein the imidazoline derivative is amphoteric glycinate.

[0200] 22. The composition of any of embodiments 1-21, wherein the second surfactant is a sulfonate surfactant, or in other words, the second surfactant comprises a sulfonate group.

[0201] 23. The composition of embodiment 22, wherein the sulfonate is linear dodecylbenzenesulfonate sodium salt.

[0202] 24. The composition of embodiment 22, wherein the sulfonate is C 14 -C 16 Olefin sulfonic acid sodium salt.

[0203] 25. The composition of embodiment 22, wherein the sulfonate is branched dodecylbenzene sulfonate sodium salt.

[0204] 26. The composition of embodiment 22, wherein the sulfonate is linear or branched triethanolamine dodecylbenzenesulfonate.

[0205] 27. A composition as described in embodiment 22, wherein the sulfonate is linear or branched dodecylbenzenesulfonic acid isopropylamine salt.

[0206] 28. The composition of any of embodiments 1-21, wherein the second surfactant is a sulfate salt, or in other words, the second surfactant comprises a sulfate group.

[0207] 29. The composition of embodiment 28, wherein the sulfate salt is sodium lauryl ether sulfate.

[0208] 30. The composition of embodiment 28, wherein the sulfate salt is ammonium lauryl sulfate.

[0209] 31. The composition of embodiment 28, wherein the sulfate salt is sodium octyl sulfate.

[0210] 32. The composition of embodiment 28, wherein the sulfate salt is sodium lauryl sulfate.

[0211] 33. A composition as described in embodiment 28, wherein the sulfate is an ethoxylated C6-C 12 Alcohol sodium salt.

[0212] 34. The composition of embodiment 28, wherein the sulfate is sodium laureth sulfate.

[0213] 35. A composition as described in embodiment 28, wherein the sulfate is C 12 -C 14 Sodium sulfate, tert-alkyl ethoxylate.

[0214] 36. The composition of any of embodiments 1-21, wherein the second surfactant is a sulfoacetate surfactant.

[0215] 37. The composition of embodiment 36, wherein the sulfoacetate is sodium lauryl sulfoacetate.

[0216] 38. The composition of embodiment 36, wherein the sulfoacetate salt is hexadecyl ammonium sulfoacetate salt.

[0217] 39. The composition of any of embodiments 1-21, wherein the second surfactant is a phosphate ester surfactant selected from phosphate monoester and phosphate diester surfactants.

[0218] 40. The composition of embodiment 39, wherein the phosphate ester is polyoxyethylene (10) nonylphenol phosphate.

[0219] 41. A composition as described in embodiment 39, wherein the phosphate ester is C8H 17 Phosphate sodium salt.

[0220] 42. The composition of any of embodiments 1-21, wherein the second surfactant is a sulfosuccinate surfactant.

[0221] 43. The composition of embodiment 42, wherein the sulfosuccinate salt is dioctyl sodium sulfosuccinate.

[0222] 44. The composition of embodiment 42, wherein the sulfosuccinate salt is disodium laureth sulfosuccinate.

[0223] 45. The composition of any of embodiments 1-21, wherein the second surfactant is a carboxylate.

[0224] 46. ​​The composition of embodiment 45, wherein the carboxylate salt is polyoxyethylene (8) octyl ether carboxylate sodium salt.

[0225] 47. The composition of embodiment 45, wherein the carboxylate salt is sodium stearate.

[0226] 48. The composition of any of embodiments 1-21, wherein the second surfactant is sarcosinate.

[0227] 49. The composition of embodiment 48, wherein the sarcosinate is sodium lauroyl sarcosinate.

[0228] 50. The composition of embodiment 48, wherein the sarcosinate is ammonium cocoyl sarcosinate.

[0229] 51. The composition of any of embodiments 1-21, wherein the second surfactant is a diphenyl oxide surfactant.

[0230] 52. A composition as described in embodiment 51, wherein the diphenyl oxide is a linear decyl substituted bissulfonated diphenyl oxide sodium salt.

[0231] 53. A composition as described in embodiment 51, wherein the diphenyl oxide is a branched dodecyl-substituted bissulfonated diphenyl oxide.

[0232] 54. The composition of embodiment 1, wherein the first surfactant comprises a betaine and the second surfactant comprises a sulfonate.

[0233] 55. The composition of embodiment 54, wherein the first surfactant is an amidopropyl betaine surfactant, optionally cocamidopropyl betaine, and the second surfactant is an alkylaryl sulfonate surfactant, optionally dodecylbenzene sulfonate.

[0234] 56. The composition of embodiment 1, wherein the first surfactant comprises an amphoacetate and the second surfactant comprises a sulfonate.

[0235] 57. The composition of embodiment 1, wherein the first surfactant comprises hydroxysulfobetaine and the second surfactant comprises sulfoacetate.

[0236] 58. A composition as described in embodiment 1, wherein the first surfactant comprises an amphoteric dipropionate and the second surfactant comprises a phosphate ester.

[0237] 59. A composition as described in embodiment 1, wherein the first surfactant comprises an amine oxide and the second surfactant comprises a carboxylic acid, such as a carboxylate.

[0238] 60. The composition of embodiment 1, wherein the first surfactant comprises a betaine and the second surfactant comprises a carboxylic acid, eg, a carboxylate.

[0239] 61. The composition as described in each of embodiments 54-60, which further comprises an inorganic salt and a thickener as solid components.

[0240] 62. The composition of any of embodiments 54-60, comprising a single amphoteric surfactant, a single anionic surfactant, an inorganic salt, and a thickener.

[0241] 63. A composition as described in any of embodiments 1-62, wherein the amphoteric surfactant accounts for 10-30 wt% of the weight of the solid component.

[0242] 64. A composition as described in any of embodiments 1-62, wherein the amphoteric surfactant accounts for 15-25 wt% of the weight of the solid components.

[0243] 65. The composition of any one of embodiments 1-62, wherein the anionic surfactant comprises 31-60 wt % of the weight of the solid components.

[0244] 66. A composition as described in any of embodiments 1-62, wherein the anionic surfactant accounts for 40-50 wt% of the weight of the solid component.

[0245] 67. A composition as described in any of embodiments 1-62, wherein the amphoteric surfactant accounts for 15-25 wt% of the solid component and the anionic surfactant accounts for 40-50 wt% of the solid component.

[0246] 68. A composition as described in any of embodiments 1-62, wherein the wt% of the anionic surfactant is 1.5 to 3 times the wt% of the amphoteric surfactant based on the total weight of surfactants present in the composition.

[0247] 69. A composition as described in any of embodiments 1-62, wherein the wt% of the anionic surfactant is 1.5 to 2.5 times the wt% of the amphoteric surfactant based on the total weight of surfactants present in the composition.

[0248] 70. A composition as described in any of embodiments 1-62, wherein the amphoteric surfactant accounts for 15-25 wt% of the solid component, the anionic surfactant accounts for 40-50 wt% of the solid component, and the inorganic salt accounts for 5-20 wt% of the solid component.

[0249] 71. A composition as described in any of embodiments 1-62, wherein the amphoteric surfactant accounts for 15-25wt% of the solid component, the anionic surfactant accounts for 40-50wt% of the solid component, and the inorganic salt accounts for 5-20wt% of the solid component, and the remaining solid components are thickeners.

[0250] 72. The composition of any of the preceding embodiments, comprising an inorganic salt, wherein the inorganic salt is optionally calcium chloride.

[0251] 73. The composition of any of the preceding embodiments, comprising an aqueous thickener selected from polyamides and cellulosic thickeners.

[0252] 74. The composition of embodiment 73, wherein the aqueous thickener is selected from carboxymethyl cellulose and hydroxyethyl cellulose.

[0253] 75. An intermittent method for preparing a fire extinguishing concentrate composition, comprising adding hot water, anionic surfactant, amphoteric surfactant, inorganic salt and thickener to a container; wherein after adding the components to the container, the obtained mixture is stirred to provide a uniform or nearly uniform mixture before adding the next component.

[0254] 76. An intermittent method for preparing a fire extinguishing concentrate composition as described in embodiment 75, comprising: a) heating water to about 70-80°C to provide hot water; b) adding anionic surfactant to the hot water; c) adding amphoteric surfactant to the mixture of step b); d) adding hot water to the mixture of step c); e) adding an inorganic salt to the mixture of step d); f) cooling the mixture of step e) to within ±20°C of ambient temperature; and g) adding a thickener to the mixture of step f); wherein after adding the components, the obtained mixture is stirred for about 30 minutes to obtain a uniform or nearly uniform mixture before adding the next component, wherein a minimum amount of foam is generated.

[0255] 77. A continuous method for preparing a fire extinguishing concentrate composition, comprising: providing a continuous reactor, injecting water into the continuous reactor, continuously supplying a) anionic surfactant, b) amphoteric surfactant to the continuous reactor, and mixing components a) and b) to provide a uniform mixture.

[0256] 78. The continuous method of embodiment 77, further comprising continuously supplying an inorganic salt and a thickener to the reactor.

[0257] 79. The continuous process of embodiment 78, wherein the inorganic salt and the thickener are added to the reactor after all of the surfactant has been added.

[0258] 80. The continuous process of embodiment 77, wherein the water in the continuous reactor is maintained at a temperature exceeding 50°C.

[0259] 81. The continuous process of embodiment 77, wherein a mixer selected from a pipeline mixer and a static mixer is present in the continuous reactor.

[0260] 82. The continuous process of embodiment 77, wherein the continuous reactor is a tank or tube of predetermined diameter and length.

[0261] 83. A method of extinguishing a fire comprising applying to the fire a composition comprising the composition of any one of embodiments 1-74 in an amount and for a time effective to extinguish the fire.

[0262] In addition, the present disclosure includes the following numbered embodiments, which are also merely exemplary and do not limit the different embodiments of the present disclosure:

[0263] 1) A composition comprising water and dissolved or suspended solids, wherein the solids comprise a first surfactant selected from amphoteric surfactants, a second surfactant selected from anionic surfactants, and a third surfactant selected from amphoteric surfactants and anionic surfactants, wherein the third surfactant is different from the first surfactant and the second surfactant.

[0264] 2) A composition as described in embodiment 1, wherein the first surfactant is a betaine surfactant, or in other words, a surfactant comprising a betaine group.

[0265] 3) A composition as described in embodiment 1, wherein the first surfactant is amidopropyl betaine.

[0266] 4) A composition as described in embodiment 3, wherein the amidopropyl betaine is cocoamidopropyl betaine.

[0267] 5) A composition as described in embodiment 3, wherein the amidopropyl betaine is isostearylpropyl betaine.

[0268] 6) A composition as described in embodiment 3, wherein the amidopropyl betaine is lauroamidopropyl betaine.

[0269] 7) A composition as described in embodiment 1, wherein the first surfactant is an amphoteric acetate surfactant.

[0270] 8) A composition as described in embodiment 7, wherein the amphoacetate is sodium cocoamphoacetate.

[0271] 9) A composition as described in embodiment 7, wherein the amphoacetate is sodium lauroamphoacetate.

[0272] 10) A composition as described in embodiment 1, wherein the first surfactant is an amphoteric propionate surfactant.

[0273] 11) A composition as described in embodiment 10, wherein the amphoteric propionate is disodium cocoamphodipropionate.

[0274] 12) A composition as described in embodiment 10, wherein the amphoteric propionate is sodium capryloylamphopropionate.

[0275] 13) A composition as described in embodiment 1, wherein the first surfactant is a hydroxysulfonate surfactant.

[0276] 14) A composition as described in embodiment 13, wherein the hydroxysultaine is cocamidopropyl hydroxysultaine.

[0277] 15) A composition as described in embodiment 13, wherein the hydroxysulfonyl betaine is oleamidopropyl hydroxysulfonyl betaine.

[0278] 16) A composition as described in embodiment 13, wherein the hydroxysulfonyl betaine is lauryl hydroxysulfonyl betaine.

[0279] 17) A composition as described in embodiment 1, wherein the first surfactant is an amine oxide surfactant.

[0280] 18) A composition as described in embodiment 17, wherein the amine oxide is cocamidopropyl amine oxide.

[0281] 19) A composition as described in embodiment 17, wherein the amine oxide is N,N-(dihydroxyethyl)myristylamine oxide.

[0282] 20) A composition as described in embodiment 1, wherein the first surfactant is an imidazoline derivative.

[0283] 21) A composition as described in embodiment 20, wherein the imidazoline derivative is amphoteric glycinate.

[0284] 22) A composition as described in each of embodiments 1-21, wherein the second surfactant is a sulfonate surfactant, or in other words, the second surfactant contains a sulfonate group.

[0285] 23) A composition as described in embodiment 22, wherein the sulfonate is linear dodecylbenzenesulfonate sodium salt.

[0286] 24) A composition as described in embodiment 22, wherein the sulfonate is C 14 -C 16 Olefin sulfonic acid sodium salt.

[0287] 25) A composition as described in embodiment 22, wherein the sulfonate is branched dodecylbenzene sulfonate sodium salt.

[0288] 26) A composition as described in embodiment 22, wherein the sulfonate is a linear or branched triethanolamine dodecylbenzenesulfonate salt.

[0289] 27) A composition as described in embodiment 22, wherein the sulfonate is a linear or branched dodecylbenzenesulfonic acid isopropylamine salt.

[0290] 28) A composition as described in each of embodiments 1-21, wherein the second surfactant is a sulfate, or in other words, the second surfactant contains sulfate groups.

[0291] 29) A composition as described in embodiment 28, wherein the sulfate is sodium lauryl ether sulfate.

[0292] 30) A composition as described in embodiment 28, wherein the sulfate is ammonium lauryl sulfate.

[0293] 31) A composition as described in embodiment 28, wherein the sulfate is sodium octyl sulfate.

[0294] 32) A composition as described in embodiment 28, wherein the sulfate is sodium dodecyl sulfate.

[0295] 33) A composition as described in embodiment 28, wherein the sulfate is an ethoxylated C6-C 12 Alcohol sodium salt.

[0296] 34) A composition as described in embodiment 28, wherein the sulfate is sodium laureth sulfate.

[0297] 35) A composition as described in embodiment 28, wherein the sulfate is C 12 -C 14 Sodium sulfate, tert-alkyl ethoxylate.

[0298] 36) A composition as described in embodiments 1-21, wherein the second surfactant is a sulfoacetate surfactant.

[0299] 37) A composition as described in embodiment 36, wherein the sulfoacetate is sodium lauryl sulfoacetate.

[0300] 38) A composition as described in embodiment 36, wherein the sulfoacetate is hexadecyl ammonium sulfoacetate.

[0301] 39) A composition as described in each of embodiments 1-21, wherein the second surfactant is a phosphate ester surfactant selected from phosphate monoester and phosphate diester surfactants.

[0302] 40) A composition as described in embodiment 39, wherein the phosphate ester is polyoxyethylene (10) nonylphenol phosphate.

[0303] 41) A composition as described in embodiment 39, wherein the phosphate ester is C8H 17 Phosphate sodium salt.

[0304] 42) A composition as described in embodiments 1-21, wherein the second surfactant is a sulfosuccinate surfactant.

[0305] 43) A composition as described in embodiment 42, wherein the sulfosuccinate is dioctyl sodium sulfosuccinate.

[0306] 44) A composition as described in embodiment 42, wherein the sulfosuccinate is disodium lauryl polyether sulfosuccinate.

[0307] 45) A composition as described in embodiments 1-21, wherein the second surfactant is a carboxylate.

[0308] 46) A composition as described in embodiment 45, wherein the carboxylate is polyoxyethylene (8) octyl ether carboxylic acid sodium salt.

[0309] 47) A composition as described in embodiment 45, wherein the carboxylate salt is sodium stearate.

[0310] 48) A composition as described in embodiments 1-21, wherein the second surfactant is sarcosinate.

[0311] 49) A composition as described in embodiment 48, wherein the sarcosinate is sodium lauroyl sarcosinate.

[0312] 50) A composition as described in embodiment 48, wherein the sarcosinate is ammonium cocoyl sarcosinate.

[0313] 51) A composition as described in embodiments 1-21, wherein the second surfactant is a diphenyl oxide surfactant.

[0314] 52) A composition as described in embodiment 51, wherein the diphenyl oxide is a linear decyl substituted disulfonated diphenyl oxide sodium salt.

[0315] 53) A composition as described in embodiment 51, wherein the diphenyl oxide is a branched dodecyl-substituted disulfonated diphenyl oxide.

[0316] 54) A composition as described in embodiments 1-53, wherein the third surfactant is an anionic surfactant.

[0317] 55) A composition as described in embodiment 54, wherein the second surfactant and the third surfactant are different and are each selected from the following groups: surfactants containing sulfonates, surfactants containing sulfates, surfactants containing sulfoacetates, surfactants containing phosphates, surfactants containing sulfosuccinates, surfactants containing carboxylates, surfactants containing sarcosinates, and surfactants containing diphenyl oxides.

[0318] 56) A composition as described in embodiment 1, wherein the first surfactant comprises betaine, the second surfactant comprises sulfonate, and the third surfactant comprises sulfate.

[0319] 57) A composition as described in embodiment 56, wherein the first surfactant is an amidopropyl betaine surfactant, optionally cocoamidopropyl betaine, the second surfactant is an alkyl aryl sulfonate surfactant, optionally dodecylbenzene sulfonate, and the third surfactant comprises a sulfate surfactant, optionally selected from laureth sulfate, octyl sulfate and dodecyl sulfate.

[0320] 58) A composition as described in embodiment 1, wherein the first surfactant comprises amphoteric acetate, the second surfactant comprises sulfonate, and the third surfactant comprises sulfate.

[0321] 59) A composition as described in embodiment 1, wherein the first surfactant comprises hydroxysulfobetaine, the second surfactant comprises sulfoacetate, and the third surfactant comprises sulfate.

[0322] 60) A composition as described in embodiment 1, wherein the first surfactant comprises amphoteric dipropionate, the second surfactant comprises phosphate, and the third surfactant comprises sulfosuccinate.

[0323] 61) A composition as described in embodiment 1, wherein the first surfactant comprises an amine oxide, the second surfactant comprises a carboxylic acid, and the third surfactant comprises a sarcosinate.

[0324] 62) A composition as described in embodiment 1, wherein the first surfactant comprises betaine, the second surfactant comprises carboxylate, and the third surfactant comprises disulfonated diphenyl oxide.

[0325] 63) A composition as described in each of embodiments 54-62, which also contains an inorganic salt, a thickener and an organic solvent selected from ethylene glycol monoether and ethylene glycol diether.

[0326] 64) A composition as described in embodiments 1-53, wherein the third surfactant is an amphoteric surfactant.

[0327] 65) A composition as described in embodiment 64, wherein the third surfactant is an amidopropyl betaine amphoteric surfactant.

[0328] 66) A composition as described in any of embodiments 1-3 and 5-53, wherein the third surfactant is cocamidopropyl betaine.

[0329] 67) A composition as described in any of embodiments 1-4 and 6-53, wherein the third surfactant is isostearylpropyl betaine.

[0330] 68) A composition as described in any of embodiments 1-5 and 7-53, wherein the third surfactant is lauroamidopropyl betaine.

[0331] 69) A composition as described in any of embodiments 1-53, wherein the third surfactant is an amphoteric acetate amphoteric surfactant.

[0332] 70) A composition as described in any of embodiments 1-7 and 9-53, wherein the third surfactant is sodium cocoamphoacetate.

[0333] 71) A composition as described in any of embodiments 1-8 and 10-53, wherein the third surfactant is sodium lauroamphoacetate.

[0334] 72) A composition as described in any of embodiments 1-53, wherein the third surfactant is an amphoteric propionate amphoteric surfactant.

[0335] 73) A composition as described in any of embodiments 1-10 and 12-53, wherein the third surfactant is disodium cocoamphodipropionate.

[0336] 74) A composition as described in any of embodiments 1-11 and 13-53, wherein the third surfactant is sodium capryloylamphopropionic acid salt.

[0337] 75) A composition as described in any of embodiments 1-53, wherein the third surfactant is a hydroxysulfonyl betaine amphoteric surfactant.

[0338] 76) A composition as described in any of embodiments 1-13 and 15-53, wherein the third surfactant is cocamidopropyl hydroxysultaine.

[0339] 77) A composition as described in any of embodiments 1-14 and 16-53, wherein the third surfactant is oleamidopropyl hydroxysulfonate.

[0340] 78) A composition as described in any of embodiments 1-15 and 17-53, wherein the third surfactant is lauryl hydroxysulfonobetaine.

[0341] 79) A composition as described in any of embodiments 1-53, wherein the third surfactant is an amine oxide amphoteric surfactant.

[0342] 80) A composition as described in any of embodiments 1-17 and 19-53, wherein the third surfactant is cocamidopropylamine oxide.

[0343] 81) A composition as described in any of embodiments 1-18 and 20-53, wherein the third surfactant is N,N-(dihydroxyethyl)myristylamine oxide.

[0344] 82) A composition as described in any of embodiments 1-53, wherein the third surfactant is an imidazoline derivative amphoteric surfactant.

[0345] 83) A composition as described in any of embodiments 1-53, wherein the third surfactant is an amphoteric glycinate amphoteric surfactant.

[0346] 84) A composition as described in any of embodiments 1-53, wherein the third surfactant is an anionic surfactant comprising a sulfonate.

[0347] 85) A composition as described in any of embodiments 1-22 and 24-53, wherein the third surfactant is linear dodecylbenzene sulfonate sodium salt.

[0348] 86) A composition as described in any one of embodiments 1-23 and 25-53, wherein the third surfactant is C 14 -C 16 Olefin sulfonic acid sodium salt.

[0349] 87) A composition as described in any of embodiments 1-24 and 26-53, wherein the third surfactant is branched dodecylbenzene sulfonate sodium salt.

[0350] 88) A composition as described in any of embodiments 1-25 and 27-53, wherein the third surfactant is a linear or branched triethanolamine salt of dodecylbenzenesulfonate.

[0351] 89) A composition as described in any of embodiments 1-26 and 28-53, wherein the third surfactant is a linear or branched isopropylamine salt of dodecylbenzenesulfonate.

[0352] 90) A composition as described in any of embodiments 1-53, wherein the third surfactant is a sulfate anionic surfactant.

[0353] 91) A composition as described in any of embodiments 1-28 and 30-53, wherein the third surfactant is sodium lauryl ether sulfate.

[0354] 92) A composition as described in any of embodiments 1-29 and 31-53, wherein the third surfactant is ammonium lauryl sulfate.

[0355] 93) A composition as described in any one of embodiments 1-34 and 36-53, wherein the third surfactant is C 12 -C 14 Sodium sulfate, tert-alkyl ethoxylate.

[0356] 94) A composition as described in any of embodiments 1-53, wherein the third surfactant is a sulfoacetate anionic surfactant.

[0357] 95) A composition as described in any of embodiments 1-36 and 38-53, wherein the third surfactant is sodium lauryl sulfoacetic acid.

[0358] 96) A composition as described in any of embodiments 1-37 and 39-53, wherein the third surfactant is hexadecyl ammonium sulfoacetate.

[0359] 97) A composition as described in any of embodiments 1-53, wherein the third surfactant is a phosphate ester anionic surfactant selected from phosphate monoester and phosphate diester surfactants.

[0360] 98) A composition as described in any of embodiments 1-39 and 41-53, wherein the third surfactant is polyoxyethylene (10) nonylphenol phosphate.

[0361] 99) A composition as described in any one of embodiments 1-40 and 42-53, wherein the third surfactant is C8H 17 Phosphate sodium salt.

[0362] 100) A composition as described in any of embodiments 1-53, wherein the third surfactant is a sulfosuccinate anionic surfactant.

[0363] 101) A composition as described in any of embodiments 1-42 and 43-53, wherein the third surfactant is dioctyl sodium sulfosuccinate.

[0364] 102) A composition as described in any of embodiments 1-43 and 44-53, wherein the third surfactant is disodium laureth sulfosuccinate.

[0365] 103) A composition as described in any of embodiments 1-53, wherein the third surfactant is a carboxylate anionic surfactant.

[0366] 104) A composition as described in any of embodiments 1-45 and 47-53, wherein the third surfactant is polyoxyethylene (8) octyl ether carboxylic acid sodium salt.

[0367] 105) A composition as described in any of embodiments 1-46 and 48-53, wherein the third surfactant is sodium stearate.

[0368] 106) A composition as described in any of embodiments 1-53, wherein the third surfactant is a sarcosinate anionic surfactant.

[0369] 107) A composition as described in any of embodiments 1-48 and 50-53, wherein the third surfactant is sodium lauroyl sarcosinate.

[0370] 108) A composition as described in any of embodiments 1-49 and 51-53, wherein the third surfactant is ammonium cocoyl sarcosinate.

[0371] 109) A composition as described in any of embodiments 1-53, wherein the third surfactant is a diphenyl oxide anionic surfactant.

[0372] 110) A composition as described in any of embodiments 1-51 and 53, wherein the third surfactant is a linear decyl substituted disulfonated diphenyl oxide sodium salt.

[0373] 111) A composition as described in any of embodiments 1-52, wherein the third surfactant is a branched dodecyl-substituted disulfonated diphenyl oxide.

[0374] 112) A composition as described in any of the preceding embodiments, wherein the amphoteric surfactant accounts for 10-30 wt% of the solid weight.

[0375] 113) A composition as described in any of the preceding embodiments, wherein the amphoteric surfactant accounts for 10-15 wt% of the solid weight.

[0376] 114) A composition as described in any of the preceding embodiments, wherein the amphoteric surfactant accounts for 15-20 wt% of the solid weight.

[0377] 115) A composition as described in any of the preceding embodiments, wherein the amphoteric surfactant accounts for 20-25 wt% of the solid weight.

[0378] 116) A composition as described in any of the preceding embodiments, wherein the amphoteric surfactant accounts for 15-25 wt% of the solid weight.

[0379] 117) A composition as described in any of the preceding embodiments, wherein the anionic surfactant accounts for 45-85 wt% of the solid weight.

[0380] 118) A composition as described in any of the preceding embodiments, wherein the anionic surfactant accounts for 45-85 wt% of the solid weight.

[0381] 119) A composition as described in any of the preceding embodiments, wherein the anionic surfactant accounts for 45-55 wt% of the weight of the solid.

[0382] 120) A composition as described in any of the preceding embodiments, wherein the anionic surfactant accounts for 55-65 wt% of the solid weight.

[0383] 121) A composition as described in any of the preceding embodiments, wherein the anionic surfactant accounts for 65-75 wt% of the solid weight.

[0384] 122) A composition as described in any of the preceding embodiments, wherein the anionic surfactant accounts for 75-85 wt% of the solid weight.

[0385] 123) A composition as described in any of the preceding embodiments, wherein the water accounts for 75-95 wt% of the composition.

[0386] 124) A composition as described in any of the preceding embodiments, wherein the water accounts for 75-80 wt% of the composition.

[0387] 125) A composition as described in any of the preceding embodiments, wherein the water accounts for 80-85 wt% of the composition.

[0388] 126) A composition as described in any of the preceding embodiments, wherein the water accounts for 85-90 wt% of the composition.

[0389] 127) A composition as described in any of the preceding embodiments, wherein the water accounts for 90-95 wt% of the composition.

[0390] 128) The composition as described in any of the preceding embodiments further comprises an inorganic salt.

[0391] 129) A composition as described in embodiment 128, wherein the inorganic salt accounts for 2wt% to 20wt% of the solid.

[0392] 130) A composition as described in embodiment 128, wherein the inorganic salt accounts for 0.1 wt% to 5.0 wt% of the composition.

[0393] 131) A composition as described in any of embodiments 128-130, wherein the inorganic salt is one or more selected from the following: basic aluminum oxalate, ammonium aluminum sulfate, aluminum borate whisker, aluminum dihydrogen phosphate, aluminum hydroxide, ammonium molybdate, aluminum phosphate, potassium aluminum sulfate, aluminum sulfate, ammonium heptamolybdate, ammonium octamolybdate, antimony trioxide, barium metaborate, barium sulfate, basic copper carbonate, basic zinc carbonate, beryllium carbonate, bismuth hydroxide, calcium carbonate, calcium chloride, calcium hydrogen phosphate, cerium hydroxide, Cerium carbonate, chromium carbonate, cobalt hydroxide, cobalt carbonate, dimanganese hydrogen phosphate, disodium hydrogen phosphate, dizinc hydrogen phosphate, dolomite (calcium magnesium hydrogen carbonate), dysprosium carbonate, erbium carbonate, europium carbonate, iron hydroxide, ferrocene, ferric acetone, iron oxide, ferroferric oxide, ferrous ammonium sulfate, ferrous carbonate, gadolinium carbonate, guanidine carbonate, holmium carbonate, strontium hydrogen phosphate metaborate, strontium hydrogen phosphate potassium metaborate, hydromagnesite, iron nitride, lanthanum carbonate, lanthanum hydroxide, lithium carbonate, lutetium carbonate, magnesium ammonium phosphate, manganese borate, Magnesium dihydrogen phosphate, magnesium hydrogen phosphate, magnesium hydrogen sulfate, magnesium hydroxide, magnesium metaborate hydrate, magnesium nitrate, magnesium trisilicate, manganese carbonate, manganese citrate, manganese dihydrogen phosphate, manganese oxalate dihydrate, manganese phosphate, manganese tungstate, manganite, molybdenum hydroxide, monocalcium phosphate, monopotassium phosphate, neodymium carbonate, nickel carbonate, nickel oxalate, potassium bicarbonate, potassium hexafluorotitanate, potassium hexafluorozirconate, potassium metaphosphate, potassium nitrate, potassium oxalate, potassium sodium carbonate hexahydrate, potassium tetraborate hydrate, potassium tripolyphosphate, praseodymium carbonate, carbon samarium carbonate, scandium carbonate, silver carbonate, sodium bicarbonate, sodium citrate, sodium dihydrogen phosphate, sodium nitrate, sodium oxalate, sodium sesquicarbonate, sodium trimetaphosphate, sodium tungstate, strontium carbonate, strontium hydroxide, strontium metaborate, strontium tetraborate, strontium tetraborate hydrate, telluric acid, terbium carbonate, thulium carbonate, tin oxide, titanium dioxide, vanadium carbonate, ytterbium carbonate, yttrium carbonate, zinc oxide, zinc sulfide, zinc sulfate heptahydrate, zinc borate, zinc carbonate, zinc dihydrogen phosphate, zinc phosphate, zinc stannate, zirconium carbonate and zirconium nitrate.

[0394] 132) A composition as described in any of embodiments 128-130, wherein the inorganic salt is calcium chloride.

[0395] 133) The composition as described in any of the preceding embodiments further comprises an aqueous thickener.

[0396] 134) A composition as described in embodiment 133, wherein the thickener accounts for 0.1 wt% to 5 wt% of the solids.

[0397] 135) A composition as described in embodiment 133, wherein the thickener accounts for 0.01 wt% to 2 wt% of the composition.

[0398] 136) A composition as described in embodiment 133, wherein the aqueous thickener is one or more thickeners selected from polyamide and cellulosic materials.

[0399] 137) A composition as described in embodiment 133, wherein the aqueous thickener is selected from carboxymethyl cellulose and hydroxyethyl cellulose.

[0400] 138) An intermittent method for preparing a fire extinguishing concentrate composition, comprising: adding hot water, a first anionic surfactant, a second anionic surfactant, a third surfactant selected from amphoteric surfactants and anionic surfactants to a container, wherein the third surfactant is different from the first surfactant and the second surfactant, and optionally adding an inorganic salt and a thickener; wherein after adding the components to the container, the obtained mixture is stirred for about 30 minutes before adding the next component, wherein a minimum amount of foam is generated.

[0401] 139) An intermittent method for preparing a fire extinguishing concentrate composition as described in Embodiment 138, comprising: a) heating water to about 70-80°C to provide hot water; b) adding a first anionic surfactant to the hot water; c) adding a first amphoteric surfactant to the mixture of step b); d) adding hot water to the mixture of step c); e) adding a third surfactant to the mixture of step d), wherein the third surfactant is selected from anionic surfactants and amphoteric surfactants, and the third surfactant is different from the first anionic surfactant and the first amphoteric surfactant; f) adding an inorganic salt to the mixture of step e); g) cooling the mixture of step f) to within ±20°C of ambient temperature; and h) adding a thickener to the mixture of step f); wherein after adding the components, the obtained mixture is stirred for about 30 minutes before adding the next component, wherein a minimum amount of foam is generated.

[0402] 140) A continuous method for preparing a fire extinguishing concentrate composition, comprising: providing a continuous reactor, injecting water into the continuous reactor, continuously supplying a) anionic surfactant, b) amphoteric surfactant and c) a third surfactant selected from anionic surfactants and amphoteric surfactants to the continuous reactor, wherein the third surfactant is different from the anionic surfactant of step a) and the amphoteric surfactant of step b); and mixing components a), b) and c) to provide a uniform mixture.

[0403] 141) The continuous method as described in embodiment 140 also includes continuously supplying inorganic salts and thickeners to the reactor.

[0404] 142) A continuous method as described in embodiment 140, wherein the inorganic salt and the thickener are added to the reactor after all of the surfactants are added.

[0405] 143) A continuous method as described in embodiment 140, wherein the water in the continuous reactor is maintained at a temperature exceeding 50°C.

[0406] 144) A continuous method as described in embodiment 140, wherein a mixer selected from a pipeline mixer and a static mixer is present in the continuous reactor.

[0407] 145) A continuous method as described in embodiment 140, wherein the continuous reactor is a tank or tube with a predetermined diameter and length.

[0408] 146) A method of extinguishing a fire, comprising applying a composition comprising the composition of any one of embodiments 1-145 to a fire in an amount and for a time effective to extinguish the fire.

[0409] Any of the different embodiments described above can be combined to provide other embodiments. All U.S. patents, U.S. patent application disclosures, U.S. patent applications, foreign patents, foreign patent applications, and non-patent disclosures (including but not limited to [insert list]) mentioned in this specification and / or listed in the application data sheet are incorporated herein by reference in their entirety. If it is necessary to adopt the concepts of various patents, applications, and disclosures to provide other embodiments, the aspects of the embodiments can be modified. These and other changes can be made to the embodiments according to the above detailed description. Generally, in the following claims, the terms used should not be interpreted as limiting the claims to the specific embodiments disclosed in this specification and the claims, but should be interpreted as including all possible embodiments together with the full range of equivalents specified by the claims. Therefore, the claims are not limited to this disclosure.

Claims

1. A composition comprising water and a solid, wherein the solid comprises a first surfactant selected from amphoteric betaine surfactants, a second surfactant selected from dodecylbenzene sulfonate surfactants, and a third surfactant sodium lauryl ether sulfate, the composition further comprising calcium chloride and an aqueous thickener, wherein the composition does not contain a compound having a carbon-halogen bond.

2. The composition of claim 1, wherein the first surfactant is amidopropyl betaine.

3. The composition of claim 2, wherein the amidopropyl betaine is cocamidopropyl betaine.

4. The composition of claim 1, wherein the sulfonate is linear dodecylbenzene sulfonate sodium salt.

5. The composition of claim 1, wherein the sulfonate is branched dodecylbenzene sulfonate sodium salt.

6. The composition of claim 1, wherein the amphoteric betaine surfactant comprises 10-30 wt% based on the weight of the solids.

7. The composition of claim 1, wherein the anionic surfactant comprises 45-85 wt% based on the weight of the solids.

8. The composition of claim 1, wherein the water comprises 75-95 wt% of the composition.

9. The composition of claim 1, wherein the calcium chloride comprises 2-20 wt% of the solids.

10. The composition of claim 1, wherein the thickener comprises 0.01-2 wt% of the composition.

11. The composition of claim 1, wherein the aqueous thickener is one or more thickeners selected from polyamide and cellulosic materials.

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