Classifications

• • A—HUMAN NECESSITIES
  • A62—LIFE-SAVING; FIRE-FIGHTING
  • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
  • A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
  • A62D1/0071—Foams
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/17—Amines; Quaternary ammonium compounds
  • C08K5/19—Quaternary ammonium compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/54—Silicon-containing compounds
  • C08K5/544—Silicon-containing compounds containing nitrogen

Definitions

• surfactants and surfactant compositions are utilized in numerous industrial, commercial, home care, and personal care formulations.
• surfactants and surfactant compositions are commonly utilized in the preparation of a wide variety of surface treatments and coating compositions, e.g. to influence the characteristics of the compositions themselves as well as to provide surface effects to substrates threated with such surface treatment/coating compositions.
• polyfluoroalkyl-based surfactants and compositions thereof have been widely employed in industrial compositions as fume suppressants and etching additives, in surface treatments for imparting water and oil repellency to the surface of articles such as carpeting, upholstery, apparel, textiles, etc., as well as in many commercial products such as cleaning compositions, waxes, sealants, and foams.
• fluorinated surfactants have been utilized in numerous conventional aqueous film-forming foams (AFFFs), which have previously enjoyed widespread use in preventing, containing, and/or extinguishing fires.
• Z 1 is a siloxane moiety
• D 1 is a divalent linking group
• R is H or an unsubstituted hydrocarbyl group having from 1 to 4 carbon atoms
• each Y has formula -D-
• components (A) and (B) are present in the foam stabilizing composition in a weight ratio of from 0.5:1 to 3.5:1 (A)/(B); and/or (ii) components (A) and (B) are present in the foam stabilizing composition to provide a molar ratio of anionic groups in component (A) to cationic groups in component (B) of from 1:1 to 6.5:1.
• the present disclosure further provides an aqueous foam comprising the foam stabilizing composition, and methods relating to preparing and using the same.
• FIG. 1 shows a plot of extinction time (seconds) as a function of flow rate (mL/min) for certain embodiments of the invention as described in the examples hereof; and [0009] Figure 2 shows another plot of extinction time (seconds) as a function of flow rate (mL/min) for certain embodiments of the invention as described in the examples hereof.
• DETAILED DESCRIPTION [0010] A foam stabilizing composition (the “composition”) is provided.
• the composition may be utilized in foam compositions (i.e., foams), including aqueous foaming compositions, expanded foam compositions, concentrated foam compositions and/or foam concentrates, etc., which may be formulated and/or utilized in diverse end-use applications.
• foam compositions i.e., foams
• the composition may be utilized in an aqueous foams or similar foaming composition suitable for use in extinguishing, suppressing, and/or preventing fire.
• the composition has excellent performance properties even while being free from polyfluoroalkyl- based surfactants or other fluorine sources.
• the composition comprises (A) an anionic polymer and (B) a siloxane cationic surfactant.
• component (A) of the composition is an anionic polymer.
• the anionic polymer (A) is not limited.
• the anionic polymer (A) is soluble in water, meaning that the anionic polymer (A) can form a homogenous solution when disposed in water, optionally under shear or mixing.
• the anionic polymer (A) comprises, alternatively is, a polyelectrolyte.
• the term “polymer” and “polyelectrolyte” with reference to component (A) includes, but is not limited to, homopolymers, copolymers, such as graft, random and alternating copolymers, terpolymers, etc. and blends and modifications thereof.
• the term “polymer” and “polyelectrolyte” shall include all possible geometrical configurations of the molecule. These configurations include, but are not limited to isotactic, syndiotactic and random symmetries.
• polyelectrolyte means a polymer having at least one permanent anionic charge when dissolved in an aqueous solution.
• polyelectrolyte also means a polymer capable of forming an anionic charge, when dissolved in an aqueous solution whose pH has been adjusted by some means including the addition of an acid or suitable buffering agent, so as to form a net anionic charge on the polymer in water.
• the acidic nature of the anionic polymer (A) may be provided or imparted by a native acid moiety, or may result from the hydrolysis of one or more anhydride moieties, as in the conversion of a succinic anhydride moiety to a succinic diacid moiety.
• the anionic polymer can be any that has a carboxylic acid moiety, maleic acid moiety, acetylacetone moiety, phosphoric acid moiety, sulfonic acid moiety, salts thereof, and half esters thereof.
• Suitable anionic polymers can be exemplified by acrylate ester/methacrylate ester copolymers, vinyl acetate/crotonic acid copolymers, vinyl acetate/crotonic acid/vinyl neodecanoate copolymers, methyl vinyl ether/maleate hemiester, t-butyl acrylate/ethyl acrylate/methacrylic acid copolymers, vinylpyrrolidone/vinyl acetate/vinyl propionate copolymers, vinyl acetate/crotonic acid copolymers, vinyl acetate/crotonic acid/vinylpyrrolidone copolymers, vinylpyrrolidone/acrylate copolymers, acrylate/acrylamide copolymers, vinyl acetate/butyl maleate/isobornyl acrylate copolymers, alkanolamine acrylic resins, urethane-modified acrylic polymers, ethylene-acrylic acid copolymers,
• polymers containing monomers capable of taking on an anionic charge in aqueous solutions when dissolved in water that has been adjusted to an appropriate pH using an acid, a buffer or combination thereof include acrylic acid, maleic acid, methacrylic acid, ethacrylic acid, dimethylacrylic acid, maleic anhydride, succinic anhydride, vinylsulfonate, cyanoacrylic acid, methylenemalonic acid, vinylacetic acid, allylacetic acid, ethylidineacetic acid, propylidineacetic acid, crotonic acid, fumaric acid, itaconic acid, sorbic acid, angelic acid, cinnamic acid, styrylacrylic acid, citraconic acid, glutaconic acid, aconitic acid, phenylacrylic acid, acryloxypropionic acid, vinylbenzoic acid, N-vinylsuccinamidic acid, mesaconic acid, carboxylic acid, phosphoric acids sulfonic acid
• Suitable acid monomers also include styrenesulfonic acid, acrylamide methyl propane sulfonic acid, 2-methacryloyloxy-methane-1-sulfonic acid, 3-methacryloyloxy- propane-l-sulfonic acid, 3-(vinyloxy)-propane-1-sulfonic acid, ethylenesulfonic acid, vinyl sulfuric acid, 4-vinylphenyl sulfuric acid, ethylene phosphonic acid and vinyl phosphoric acid.
• anionic polymers including but not limited to saccharinic gums and/or polysaccharides, including alginates, xanthates, pectins, carrageenans, guar, carboxymethyl cellulose, sodium carboxymethyl cellulose, carboxymethyl dextran, sodium carboxymethyl dextra, scleroglucans, and combinations thereof.
• the anionic polymer (A) includes at least one anionic group selected from a carboxyl group, a sulfonic group, a sulfato group, a phosphonic group, and a phosphate group.
• the anionic polymer (A) comprises, alternatively is, a polysaccharide having at least one of these anionic groups.
• saccharide may be used synonymously with the term “carbohydrate” under general circumstances, and terms like “sugar” under more specific circumstances.
• suitable saccharides may include, alternatively may be, any compound comprising a moiety that can be described as a saccharide, carbohydrate, sugar, starch, cellulose, and the like, or a derivative or modification thereof, or combinations thereof.
• any combination of more than one saccharide moiety in the saccharide compounds may be described more descriptive terms.
• polysaccharide may be used synonymously with the term “glycoside,” where both terms generally refer to a combination of more than one saccharide moiety (e.g. where the combination of saccharide moieties are linked together via glycosidic linkage(s) and collectively form a glycoside moiety).
• glycoside e.g. where the combination of saccharide moieties are linked together via glycosidic linkage(s) and collectively form a glycoside moiety.
• starch and “cellulose” may be used to refer to such combinations of saccharide moieties under specific circumstances (e.g.
• examples of polysaccharides suitable for use in or as the anionic polymer (A) may include compounds, or compounds comprising two or more moieties conventionally referred to as a monosaccharide and/or sugar (e.g.
• the anionic polymer (A) may include a combination of different anionic groups.
• the anionic polymer (A) may comprise a blend or two or more different anionic polymers, which differ in terms of molecular weight, anionic content, anionic functional group, etc.
• the composition further comprises (B) a siloxane cationic surfactant, i.e., a complex comprising a cationic organosilicon compound charge-balanced with a counter ion.
• Z 1 is a siloxane moiety
• D 1 is a divalent linking group
• R is H or an unsubstituted hydrocarbyl group having from 1 to 4 carbon atoms
• Z 1 represents a siloxane moiety.
• the siloxane moiety Z 1 comprises a siloxane and is otherwise not particularly limited.
• siloxanes comprise an inorganic silicon-oxygen-silicon group (i.e., -Si-O- Si-), with organosilicon and/or organic side groups attached to the silicon atoms.
• siloxanes may be represented by the general formula ([Rx i SiO (4-i)/2 ] h ) j (Rx) 3-j Si-, where subscript i is independently selected from 1, 2, and 3 in each moiety indicated by subscript h, subscript h is at least 1, subscript j is 1, 2, or 3, and each R x is independently selected from hydrocarbyl groups, alkoxy and/or aryloxy groups, and siloxy groups.
• Hydrocarbyl groups suitable for R x include monovalent hydrocarbon moieties, as well as derivatives and modifications thereof, which may independently be substituted or unsubstituted, linear, branched, cyclic, or combinations thereof, and saturated or unsaturated.
• the term “unsubstituted” describes hydrocarbon moieties composed of carbon and hydrogen atoms, i.e., without heteroatom substituents.
• substituted describes hydrocarbon moieties where either at least one hydrogen atom is replaced with an atom or group other than hydrogen (e.g. a halogen atom, an alkoxy group, an amine group, etc.) (i.e., as a pendant or terminal substituent), a carbon atom within a chain/backbone of the hydrocarbon is replaced with an atom other than carbon (e.g. a heteroatom, such as oxygen, sulfur, nitrogen, etc.) (i.e., as a part of the chain/backbone), or both.
• an atom or group other than hydrogen e.g. a halogen atom, an alkoxy group, an amine group, etc.
• a carbon atom within a chain/backbone of the hydrocarbon e.g. a heteroatom, such as oxygen, sulfur, nitrogen, etc.
• suitable hydrocarbyl groups may comprise, or be, a hydrocarbon moiety having one or more substituents in and/or on (i.e., appended to and/or integral with) a carbon chain/backbone thereof, such that the hydrocarbon moiety may comprise, or be, an ether, an ester, etc.
• Linear and branched hydrocarbyl groups may independently be saturated or unsaturated and, when unsaturated, may be conjugated or nonconjugated.
• Cyclic hydrocarbyl groups may independently be monocyclic or polycyclic, and encompass cycloalkyl groups, aryl groups, and heterocycles, which may be aromatic, saturated and nonaromatic and/or non-conjugated, etc.
• Examples of combinations of linear and cyclic hydrocarbyl groups include alkaryl groups, aralkyl groups, etc.
• General examples of hydrocarbon moieties suitably for use in or as the hydrocarbyl group include alkyl groups, aryl groups, alkenyl groups, alkynyl groups, halocarbon groups, and the like, as well as derivatives, modifications, and combinations thereof.
• alkyl groups include methyl, ethyl, propyl (e.g. iso-propyl and/or n-propyl), butyl (e.g. isobutyl, n-butyl, tert-butyl, and/or sec- butyl), pentyl (e.g.
• aryl groups include phenyl, tolyl, xylyl, naphthyl, benzyl, dimethyl phenyl, and the like, as well as derivatives and modifications thereof, which may overlap with alkaryl groups (e.g. benzyl) and aralkyl groups (e.g. tolyl, dimethyl phenyl, etc.).
• alkenyl groups include vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, heptenyl, hexenyl, cyclohexenyl groups, and the like, as well as derivatives and modifications thereof.
• halocarbon groups include halogenated derivatives of the hydrocarbon moieties above, such as halogenated alkyl groups (e.g. any of the alkyl groups described above, where one or more hydrogen atoms is replaced with a halogen atom such as F or Cl), aryl groups (e.g.
• halogenated alkyl groups include fluoromethyl, 2- fluoropropyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl, 4,4,4,3,3-pentafluorobutyl, 5,5,5,4,4,3,3- heptafluoropentyl, 6,6,6,5,5,4,4,3,3-nonafluorohexyl, and 8,8,7,7-pentafluorooctyl, 2,2- difluorocyclopropyl, 2,3-difluorocyclobutyl, 3,4-difluorocyclohexyl, 3,4-difluoro-5- methylcycloheptyl, chloromethyl, chloropropyl, 2-dichlorocyclopropyl, 2,3-dichlorocyclopentyl
• halogenated aryl groups include chlorobenzyl, pentafluorophenyl, fluorobenzyl groups, and the like, as well as derivatives and modifications thereof.
• Alkoxy and aryloxy groups suitable for R x include those having the general formula – OR xi , where R xi is one of the hydrocarbyl groups set forth above with respect to R x .
• alkoxy groups include methoxy, ethoxy, propoxy, butoxy, benzyloxy, and the like, as well as derivatives and modifications thereof.
• aryloxy groups include phenoxy, tolyloxy, pentafluorophenoxy, and the like, as well as derivatives and modifications thereof.
• Examples of suitable siloxy groups suitable for R x include [M], [D], [T], and [Q] units, which, as understood in the art, each represent structural units of individual functionality present in siloxanes, such as organosiloxanes and organopolysiloxanes. More specifically, [M] represents a monofunctional unit of general formula R xii 3 SiO 1/2 ; [D] represents a difunctional unit of general formula R xii 2 SiO 2/2 ; [T] represents a trifunctional unit of general formula R xii SiO 3/2 ; and [Q] represents a tetrafunctional unit of general formula SiO 4/2 , as shown by the general structural moieties below: .
• each R xii is independently a monovalent or polyvalent substituent.
• substituents suitable for each R xii are not limited, and may be monoatomic or polyatomic, organic or inorganic, linear or branched, substituted or unsubstituted, aromatic, aliphatic, saturated or unsaturated, and combinations thereof.
• each R xii is independently selected from hydrocarbyl groups, alkoxy and/or aryloxy groups, and siloxy groups.
• each R xii may independently be a hydrocarbyl group of formula -R xi or an alkoxy or aryloxy group of formula -OR xi , where R xi is as defined above, or a siloxy group represented by any one, or combination, of [M], [D], [T], and/or [Q] units described above.
• the siloxane moiety Z 1 may be linear, branched, or combinations thereof, e.g. based on the number and arrangement of [M], [D], [T], and/or [Q] siloxy units present therein. When branched, the siloxane moiety Z 1 may minimally branched or, alternatively, may be hyperbranched and/or dendritic.
• the siloxane moiety Z 1 is a branched siloxane moiety having the formula -Si(R 3 ) 3 , wherein at least one R 3 is -OSi(R 4 ) 3 and each other R 3 is independently selected from R 2 and -OSi(R 4 ) 3 , where each R 4 is independently selected from R 2 , –OSi(R 5 ) 3 , and –[OSiR 2 2 ] m OSiR 2 3 .
• each R 5 is independently selected from R 2 , -OSi(R 6 ) 3 , and -[OSiR 2 2 ] m OSiR 2 3
• each R 6 is independently selected from R 2 and -[OSiR 2 2 ] m OSiR 2 3 .
• R 2 is an independently selected substituted or unsubstituted hydrocarbyl group, such as any of those described above with respect to R x
• each subscript m is individually selected such that 0 ⁇ m ⁇ 100 (i.e., in each selection where applicable).
• each R 3 is selected from R 2 and -OSi(R 4 ) 3 , with the proviso that at least one R 3 is of formula -OSi(R 4 ) 3 .
• at least two of R 3 are of formula -OSi(R 4 ) 3 .
• each R 3 is of formula -OSi(R 4 ) 3 . It will be appreciated that a greater number of R 3 being -OSi(R 4 ) 3 increases the level of branching in the siloxane moiety Z 1 .
• the silicon atom to which each R 3 is bonded is a T siloxy unit.
• R 3 when two of R 3 are of formula OSi(R 4 ) 3 , the silicon atom to which each R 3 is bonded is a [D] siloxy unit.
• R 3 when R 3 is of formula -OSi(R 4 ) 3 , and when R 4 is of formula -OSi(R 5 ) 3 , further siloxane bonds and branching are present in the siloxane moiety Z 1 .
• R 5 is of formula -OSi(R 6 ) 3 .
• each subsequent R 3+n moiety in the siloxane moiety Z 1 can impart a further generation of branching, depending on the particular selections thereof.
• R 4 can be of formula -OSi(R 5 ) 3
• R 5 can be of formula -OSi(R 6 ) 3
• further branching attributable to [T] and/or [Q] siloxy units may be present in the siloxane moiety Z 1 (i.e., beyond those of other substituents/moieties described above).
• Each R 4 is selected from R 2 , -OSi(R 5 ) 3 , and -[OSiR 2 2 ] m OSiR 2 3 , where 0 ⁇ m ⁇ 100.
• further branching can be present in the siloxane moiety Z 1 .
• each -OSi(R 4 ) 3 moiety i.e., each R 3 of formula - OSi(R 4 ) 3
• each R 3 can be written as -OSiR 2 3 (i.e., an [M] siloxy unit).
• the siloxane moiety Z 1 includes a [T] siloxy unit bonded to group D in formula (I), which [T] siloxy unit is capped by three [M] siloxy units.
• R 4 when of formula - [OSiR 2 2 ] m OSiR 2 3 , R 4 includes optional [D] siloxy units (i.e., those siloxy units in each moiety indicated by subscript m) as well as an [M] siloxy unit (i.e., represented by OSiR 2 3 ).
• each R 3 when each R 3 is of formula -OSi(R 4 ) 3 and each R 4 is of formula -[OSiR 2 2 ] m OSiR 2 3 , then each R 3 includes a [Q] siloxy unit.
• each R 3 is of formula - OSi([OSiR 2 2 ] m OSiR 2 3 ) 3 , such that when each subscript m is 0, each R 3 is a [Q] siloxy unit endcapped with three [M] siloxy units. Likewise, when subscript m is greater than 0, each R 3 includes a linear moiety (i.e., a diorganosiloxane moiety) with a degree of polymerization being attributable to subscript m. [0030] As set forth above, each R 4 can also be of formula -OSi(R 5 ) 3 .
• each R 5 is selected from R 2 , -OSi(R 6 ) 3 , and –[OSiR 2 2 ] m OSiR 2 3 , where each R 6 is selected from R 2 and -[OSiR 2 2 ] m OSiR 2 3 , and where each subscript m is defined above.
• Subscript m is from (and including) 0 to 100, alternatively from 0 to 80, alternatively from 0 to 60, alternatively from 0 to 40, alternatively from 0 to 20, alternatively from 0 to 19, alternatively from 0 to 18, alternatively from 0 to 17, alternatively from 0 to 16, alternatively from 0 to 15, alternatively from 0 to 14, alternatively from 0 to 13, alternatively from 0 to 12, alternatively from 0 to 11, alternatively from 0 to 10, alternatively from 0 to 9, alternatively from 0 to 8, alternatively from 0 to 7, alternatively from 0 to 6, alternatively from 0 to 5, alternatively from 0 to 4, alternatively from 0 to 3, alternatively from 0 to 2, alternatively from 0 to 1, alternatively is 0.
• each subscript m is 0, such that the siloxane moiety Z 1 is free from D siloxy units.
• each of R 2 , R 3 , R 4 , R 5 , and R 6 are independently selected. As such, the descriptions above relating to each of these substituents is not meant to mean or imply that each substituent is the same. Rather, any description above relating to R 4 , for example, may relate to only one R 4 or any number of R 4 in the siloxane moiety Z 1 , and so on. In addition, different selections of R 2 , R 3 , R 4 , R 5 , and R 6 can result in the same structures.
• R 3 is - OSi(R 4 ) 3
• R 4 is -OSi(R 5 ) 3
• R 5 is R 2
• R 3 can be written as - OSi(OSiR 2 3 ) 3.
• R 3 is -OSi(R 4 ) 3
• R 4 is -[OSiR 2 2 ] m OSiR 2 3
• R 3 can be written as -OSi(OSiR 2 3 ) 3 when subscript m is 0.
• these particular selections result in the same final structure for R 3 , based on different selections for R 4 .
• each R 2 is an independently selected alkyl group.
• each R 2 is an independently selected alkyl group having from 1 to 10, alternatively from 1 to 8, alternatively from 1 to 6, alternatively from 1 to 4, alternatively from 1 to 3, alternatively from 1 to 2 carbon atom(s).
• each subscript m is 0 and each R 2 is methyl, and the siloxane moiety Z 1 has one of the following structures (i)-(iv):
• D 1 a divalent linking group.
• the divalent linking group D 1 is not particularly limited.
• divalent linking group D 1 is selected from divalent hydrocarbon groups. Examples of such hydrocarbon groups include divalent forms of the hydrocarbyl and hydrocarbon groups described above, such as any of those set forth above with respect to R x . As such, it will be appreciated that suitable hydrocarbon groups for the divalent linking group D 1 may be substituted or unsubstituted, and linear, branched, and/or cyclic.
• divalent linking group D 1 comprises, alternatively is a linear or branched alkyl and/or alkylene group.
• divalent linking group D 1 comprises, alternatively is, a C 1 -C 18 hydrocarbon moiety, such as a linear hydrocarbon moiety having the formula -(CH 2 ) d -, where subscript d is from 1 to 18.
• subscript d is from 1 to 16, such as from 1 to 12, alternatively from 1 to 10, alternatively from 1 to 8, alternatively from 1 to 6, alternatively from 2 to 6, alternatively from 2 to 4.
• subscript d is 3, such that divalent linking group D 1 comprises a propylene (i.e., a chain of 3 carbon atoms).
• each unit represented by subscript d is a methylene unit, such that linear hydrocarbon moiety may be defined or otherwise referred to as an alkylene group. It will also be appreciated that each methylene group may independently be unsubstituted and unbranched, or substituted (e.g. with a hydrogen atom replaced with a non-hydrogen atom or group) and/or branched (e.g. with a hydrogen atom replaced with an alkyl group).
• divalent linking group D 1 comprises, alternatively is, an unsubstituted alkylene group. In other embodiments, divalent linking group D 1 comprises, alternatively is, a substituted hydrocarbon group, such as a substituted alkylene group.
• divalent linking group D 1 typically comprises a carbon backbone having at least 2 carbon atoms and at least one heteroatom (e.g. O, N, S, etc.), such that the backbone comprises an ether moiety, amine moiety, etc.
• divalent linking group D 1 comprises, alternatively is, an amino substituted hydrocarbon group (i.e., a hydrocarbon comprising a nitrogen-substituted carbon chain/backbone).
• the divalent linking group D 1 is an amino substituted hydrocarbon having formula -D 3 -N(R 7 )-D 3 -, such that the siloxane cationic surfactant (B) may be represented by the following formula: where each D 3 is an independently selected divalent linking group, Z 1 is as defined and described above, R 7 is Y or H, and each Y, R, subscript a, X, superscript y, superscript x, and subscript n is as defined above and described below. [0038] As introduced above, each D 3 of the amino substituted hydrocarbon divalent linking group is independently selected.
• each D 3 comprises an independently selected alkylene group, such as any of those described above with respect to divalent linking group D 1 .
• each D 3 is independently selected from alkylene groups having from 1 to 8 carbon atoms, such as from 2 to 8, alternatively from 2 to 6, alternatively from 2 to 4 carbon atoms.
• each D 3 is propylene (i.e., -(CH 2 ) 3 -).
• one or both D 3 may be, or comprise, another divalent linking group (i.e., aside from the alkylene groups described above).
• each D 3 may be substituted or unsubstituted, linear or branched, and various combinations thereof.
• R 7 of the amino substituted hydrocarbon is H or quaternary ammonium moiety Y (i.e., of formula -D-NR 1 3 + , as set forth above).
• R 7 H such that the siloxane cationic surfactant (B) may be represented by the following formula: where each D 3 and Z 1 is as defined and described above and each Y, R, subscript a, X, superscript y, superscript x, and subscript n is as defined above and described below.
• superscript y is 1 or 2, controlled by subscript a.
• the number of quaternary ammonium moieties Y will be controlled by subscript a as 1 or 2, providing a total cationic charge of +1 or +2, respectively. Accordingly, in such embodiments, superscript x will also be 1 or 2, such that the siloxane cationic surfactant (B) will be charge balanced.
• the number of quaternary ammonium moieties will include the Y of R 7 as well as the 1 or 2 quaternary ammonium moiety Y controlled by subscript a, providing a total cationic charge of +2 or +3, respectively.
• superscript x will be 1, 2, or 3, such that the siloxane cationic surfactant (B) will be charge balanced.
• R 7 is Y and the siloxane moiety Z 1 is the branched siloxane moiety described above, such that the siloxane cationic surfactant (B) may be represented by the following formula: [(R 3 ) 3 Si-D 3 -N(-D-NR 1 3 + )-D 3 -N(-D-NR 1 3 + ) a (R) 2-a ] +y [X -x ] n , where each D 3 and R 3 is as defined and described above, and each D, R, R 1 , subscript a, X, superscript y, superscript x, and subscript n is as defined above and described below. [0042] Subscript a is 1 or 2.
• subscript a indicates whether the quaternary ammonium-substituted amino moiety of the siloxane cationic surfactant (B) represented by subformula –N(Y) a (R) 2-a has one or two of quaternary ammonium groups Y (i.e., the group of subformula (-D-NR 1 3 + ).
• subscript a also indicates the number of counter anions (i.e., number of anions X, as described below) required to balance out the cationic charge from the quaternary ammonium groups Y indicated by moieties a.
• subscript a is 1, and the siloxane cationic surfactant (B) has the following formula: [ Z 1 -D 1 -N(R)-D-NR 1 3] +y [X -x ]n, where Z 1 and D 1 are as defined and described above, and each D, R, R 1 , X, superscript y, superscript x, and subscript n is as defined above and described below.
• the siloxane cationic surfactant (B) may comprise a mixture of cationic molecules that correspond to formula (I) but are different from one another (e.g. with respect to subscript a).
• a mixture comprising the siloxane cationic surfactant (B) may have an average value of a of from 1 to 2, such as an average value of 1.5 (e.g.
• Each R independently represents H or an unsubstituted hydrocarbyl group having from 1 to 4 carbon atoms, when present (e.g. when subscript a is 1). In some embodiments, R is H. In other embodiments, R an alkyl group having from 1 to 4 carbon atoms, such as from 1 to 3, alternatively from 1 to 2 carbon atom(s). For example, R may be a methyl group, an ethyl group, a propyl group (e.g.
• each R is methyl.
• Each R 1 represents an independently selected unsubstituted hydrocarbyl group having from 1 to 4 carbon atoms.
• each R 1 is independently selected from alkyl groups having from 1 to 4 carbon atoms, such as from 1 to 3, alternatively from 1 to 2 carbon atom(s).
• each R 1 is typically selected from methyl groups, ethyl groups, propyl groups (e.g.
• each R 1 is the same as each other R 1 in the cationic surfactant.
• each R 1 is methyl or ethyl.
• each R 1 is methyl.
• Each D represents an independently selected divalent linking group (“linking group D”). Typically, linking group D is selected from substituted and unsubstituted divalent hydrocarbon groups.
• linking group D comprises an alkylene group, such as one of those described above with respect to divalent linking group D 1 .
• linking group D comprises an alkylene group having from 1 to 8 carbon atoms, such as from 1 to 6, alternatively from 2 to 6, alternatively from 2 to 4 carbon atoms.
• linking group D comprises, alternatively is, a substituted hydrocarbon group, such as a substituted alkylene group.
• linking group D typically comprises a carbon backbone having at least 2 carbon atoms, and at least one heteroatom (e.g. O) in the backbone or bonded to one of the carbon atoms thereof (e.g. as a pendant substituent).
• linking group D comprises a hydroxyl-substituted hydrocarbon having formula –D ’ -CH(-(CH 2 ) e -OH)-D ’ -, where each D ’ is independently a covalent bond or a divalent linking group, and subscript e is 0 or 1.
• at least one D ’ typically comprises an independently selected alkylene group, such as any of those described above.
• each D ’ is independently selected from alkylene groups having from 1 to 8 carbon atoms, such as from 1 to 6, alternatively from 1 to 4, alternatively from 1 to 2 carbon atoms.
• each D ’ is methylene (i.e., -CH 2 -). However, it is to be appreciated that one or both D ’ may be, or comprise, another divalent linking group (i.e., aside from the alkylene groups described above).
• each linking group D is an independently selected hydroxypropylene group (i.e., where each D ’ is an independently selected from the covalent bond and methylene, with the provisos that at least one D ’ is the covalent bond when subscript e is 1, and each D ’ is methylene when subscript e is 0). Accordingly, in some such embodiments, each linking group D is independently of one of the following formulas: .
• siloxane moiety Z 1 is the branched siloxane moiety
• divalent linking group D is the amino substituted hydrocarbon where each D 3 is propylene and R 7 is H, subscript a is 1, R is H, each linking group D is a (2-hydroxy)propylene group, each R 1 is methyl, and X is a monoanion, such that the siloxane cationic surfactant (B) has the following formula: where each R 3 is as defined and described above, and X is as defined above and described below.
• the siloxane cationic surfactant (B) is configured the same as described immediately above, but with R 7 being the quaternary ammonium moiety Y, such that the siloxane cationic surfactant (B) has the following formula: where each R 3 is as defined and described above, and each X is as defined above and described below.
• dianion such that one X may be sufficient to counterbalance two or more cationic quaternary ammonium moieties Y.
• the number of anions X i.e., subscript n
• suitable anions include organic anions, inorganic anions, and combinations thereof.
• each anion X is independently selected from monoanions that are unreactive the other moieties of the cationic surfactant.
• Examples of such anions include conjugate bases of medium and strong acids, such as halide ions (e.g.
• sulfates e.g. alkyl sulfates, etc.
• sulfonates e.g. triflates, benzyl or other aryl sulfonates, etc.
• anions may also be utilized, such as phosphates, nitrates, organic anions such as carboxylates (e.g. acetates), and the like, as well as derivatives, modifications, and combinations thereof. It is to be appreciated that derivatives of such anions include polyanionic compounds comprising two or more functional groups for which the above examples are named.
• each anion X is an inorganic anion having one to three valences.
• each X is a halide anion.
• each X is chloride (i.e., Cl-).
• component (B) has at least one of the following formulas: [0055]
• the siloxane cationic surfactant (B) may comprise a combination or two or more different siloxane cationic surfactants represented by general formula (I) above that differ in at least one property such as structure, molecular weight, degree of branching, silicon and/or carbon content, number of cationic quaternary ammonium groups Y (e.g. when subscript a represents an average value), etc.
• the siloxane cationic surfactant (B) may be utilized in any amount in the composition, depending on the form of the composition prepared, a desired use thereof, other components present therein, etc.
• the siloxane cationic surfactant (B) when the composition is formulated as a concentrate, the siloxane cationic surfactant (B) will be present in higher relative amounts as compared to non-concentrated forms (e.g. aqueous foam compositions). As such, the siloxane cationic surfactant (B) may be present in the composition in any amount, such as an amount of from 0.001 to 60 wt.%, based on the total weight of the composition (i.e., wt./wt.).
• the composition comprises the siloxane cationic surfactant (B) in an amount sufficient to provide an end-use composition (i.e., any fully formulated composition comprising the foam stabilizing composition ready for a use) with from 0.01 to 1 wt.% of the siloxane cationic surfactant (B), based on the total weight of the end-use composition (i.e., an active amount of component (A) of from 0.01 to 1 wt.%).
• an end-use composition i.e., any fully formulated composition comprising the foam stabilizing composition ready for a use
• an active amount of component (A) of from 0.01 to 1 wt.%.
• component (A) is utilized in an active amount of from 0.05 to 1 wt.%, such as from 0.1 to 0.9, alternatively from 0.1 to 0.7, alternatively from 0.1 to 0.5, alternatively from 0.1 to 0.4, alternatively from 0.15 to 0.4, alternatively from 0.2 to 0.4 wt.%, based on the total weight of the composition, or an end-use composition comprising the same.
• proviso (i) is true with respect to the composition: (i) components (A) and (B) are present in the composition in a weight ratio of from 0.5:1 to 3.5:1 (A)/(B); and/or (ii) components (A) and (B) are present in the composition to provide a molar ratio of anionic groups in component (A) to cationic groups in component (B) of from 1:1 to 6.5:1.
• proviso (i) is true, i.e., components (A) and (B) are present in the foam stabilizing composition in a weight ratio of from 0.5:1 to 3.5:1 (A)/(B).
• proviso (ii) is true, i.e., components (A) and (B) are present in the foam stabilizing composition to provide a molar ratio of anionic groups in component (A) to cationic groups in component (B) of from 1:1 to 6.5:1.
• both of provisos (i) and (ii) are true.
• the composition further comprises (C) a stability enhancer other than component (B).
• the stability enhancer (C) typically includes at least one cationic moiety and/or nonionic moiety, alternatively component (C) is cationic or nonionic.
• the stability enhancer (C) comprises, alternatively is, an amphiphilic compound.
• the stability enhancer (C) may be surface active and referred to as an amphiphilic surfactant.
• the stability enhancer (C) is not surface active and is not amphiphilic.
• the stability enhancer (C) comprises is cationic and optionally includes a counter anion. Combinations of surface active and non-surface active compounds can be used together as component (C).
• the stability enhancer (C) is not a siloxane surfactant, i.e., component (C) is free from siloxane bonds.
• the stability enhancer (C) is cationic
• one specific example of the stability enhancer (C) is an organic cationic surfactant, i.e., a complex comprising a cationic quaternary organoammonium compound charge-balanced with a counter ion.
• the organic cationic surfactant can comprise a hydrocarbon moiety and one or more quaternary ammonium moieties, and conforms to general formula (II): wherein Z 2 is a substituted or unsubstituted hydrocarbyl group or a functional group; D 2 is a covalent bond or a divalent linking group; subscript b is 1 or 2; and each R, Y, superscript y, X, subscript n, and superscript x is independently selected and as defined above.
• each R, Y, superscript y, X, subscript n, and superscript x is independently selected and as defined above with respect to the siloxane cationic surfactant (B).
• siloxane cationic surfactant B
• specific selections are exemplified below with regard to these variables in formula (II) representing the organic cationic surfactant, it will be appreciated that such selections are not limiting, but rather that all description of R, Y, superscript y, X, subscript n, and superscript x, as well as variables thereof (e.g.
• Z 2 is a substituted or unsubstituted hydrocarbyl group, or a functional group, and is otherwise not particularly limited. Examples of suitable such hydrocarbyl moieties include the unsubstituted monovalent hydrocarbon moieties described above with respect to R x . As such, it will be appreciated that Z 2 may comprise, alternatively may be, linear, branched, cyclic, or combinations thereof.
• the Z 2 may comprise aliphatic unsaturation, including ethylenic and/or acetylenic unsaturation (i.e., C-C double and/or triple bonds, otherwise known as alkenes and alkynes, respectively).
• Z 2 may comprise but one such unsaturated group or, alternatively, may comprise more than one unsaturated group, which may be nonconjugated, or conjugated (e.g. when Z 2 comprises a diene, a ene-yne, diyne, etc.) and/or aromatic (e.g. when Z 2 comprises a phenyl group, benzyl group, etc.).
• Z 2 is an unsubstituted hydrocarbyl moiety having from 5 to 20 carbon atoms.
• Z 2 comprises, alternatively is, an alkyl group.
• Suitable alkyl groups include saturated alkyl groups, which may be linear, branched, cyclic (e.g. monocyclic or polycyclic), or combinations thereof.
• alkyl groups include those having the general formula C f H 2f-2g+1 , where subscript f is from 5 to 20 (i.e., the number of carbon atoms present in the alkyl group), subscript g is the number of independent rings/cyclic loops, and at least one carbon atom designated by subscript f is bonded to group D 2 in general formula (II) above.
• Examples of linear and branched isomers of such alkyl groups include those having the general formula C f H 2f+1 , where subscript f is as defined above and at least one carbon atom designated by subscript f is bonded to group D 2 in general formula (II) above.
• Examples of monocyclic alkyl groups include those having the general formula C f H 2f-1 , where subscript f is as defined above and at least one carbon atom designated by subscript f is bonded to group D 2 in general formula (II) above.
• alkyl groups include pentyl groups, hexyl groups, heptyl groups, octyl groups, nonyl groups, decyl groups, undecyl groups dodecyl groups, tridecyl groups, tetradecyl groups, pentadecyl groups, hexadecyl groups, heptadecyl groups, octadecyl groups, nonadecyl groups, and eicosyl groups, including linear, branched, and/or cyclic isomers thereof.
• pentyl groups encompass n-pentyl (i.e., a linear isomer) and cyclopentyl (i.e., a cyclic isomer), as well as branched isomers such as isopentyl (i.e., 3-methylbutyl), neopentyl (i.e., 2,2-dimethylpropy), tert-pentyl (i.e., 2-methylbutan-2-yl), sec-pentyl (i.e., pentan- 2-yl), sec-isopentyl (i.e., 3-methylbutan-2-yl) etc.), 3-pentyl (i.e., pentan-3-yl), and active pentyl (i.e., 2-methylbutyl).
• isopentyl i.e., 3-methylbutyl
• neopentyl i.e., 2,2-dimethylpropy
• tert-pentyl i
• Z 2 comprises, alternatively is, an unsubstituted linear alkyl group of formula -(CH 2 ) f-1 CH 3 , where subscript f is from 5 to 20 as described above.
• Z 2 is such an unsubstituted linear alkyl group, where subscript f is from 7 to 19, such that Z 2 is an unsubstituted linear alkyl group having from 6 to 18 carbon atoms.
• subscript b is 7, 9, 11, or 13, such that Z 2 is an unsubstituted linear alkyl group having 6, 8, 10, or 12 carbon atoms, respectively.
• a substituted hydrocarbyl group suitable for Z 2 is an alkoxy or aryloxy group.
• alkoxy groups include methoxy, ethoxy, propoxy, butoxy, benzyloxy, and the like, as well as derivatives and modifications thereof.
• aryloxy groups include phenoxy, tolyloxy, pentafluorophenoxy, and the like, as well as derivatives and modifications thereof.
• functional groups suitable for Z 2 are selected from acryloxy groups, acryl groups, acrylate groups, alcohol groups, benzene groups, epoxy groups, amino groups, cyano groups, thiol groups, cycloalkyl groups, alkyl groups, nitrogen containing groups, sulfur containing groups, oxygen containing group, phosphorous containing groups, and any combination thereof.
• Z 2 is selected from an ethylenically unsaturated group, an alkyl group, an alkoxy group, an acryloxy group, an acryloyl group, and combinations thereof.
• Subscript b is 1 or 2.
• subscript b indicates whether the quaternary ammonium-substituted amino moiety of the organic cationic surfactant represented by subformula –N(Y) b (R) 2-b has one or two of quaternary ammonium groups Y (i.e., the group of subformula (-D-NR 1 3 + ).
• subscript b also indicates the number of counter anions (i.e., number of anions X, as described below) required to balance out the cationic charge from the quaternary ammonium groups Y indicated by moieties b.
• the organic cationic surfactant may comprise a mixture of cationic molecules that correspond to formula (II) but are different from one another (e.g. with respect to subscript b).
• D 2 represents a covalent bond or a divalent linking group.
• D 2 may be referred to more particularly as the “covalent bond D 2 ” or “divalent linking group D 2 ”, e.g.
• D 2 is the covalent bond (i.e., the organic cationic surfactant comprises the covalent bond D 2 ), such that Z 2 is bonded directly to the amino N atom.
• the organic cationic surfactant may be represented by the following formula: where each Z 2 , Y, R, X, subscript b, superscript y, superscript x, and subscript n are as defined and described above.
• Z 2 is an alkyl group bonded directly to the amino N atom of the organic cationic surfactant, such that the organic cationic surfactant has the following formula: where subscript b, subscript f, Y, R, X, superscript y, superscript x, and subscript n are as defined and described above. In some such embodiments, subscript f is from 6 to 18, such as from 6 to 14, alternatively from 6 to 12. [0074] In certain embodiments, D 2 is the divalent linking group bond (i.e., the organic cationic surfactant comprises the divalent linking group D 2 ).
• the divalent linking group D 1 is not particularly limited, and is generally selected from the same groups described above with respect to divalent linking group D 1 .
• divalent linking group D 2 is typically selected from divalent hydrocarbon groups.
• hydrocarbon groups include divalent forms of the hydrocarbyl and hydrocarbon groups described above, such as any of those set forth above with respect to R x .
• suitable hydrocarbon groups for the divalent linking group D 2 may be substituted or unsubstituted, linear, branched, and/or cyclic, and the same or different from any other linking group in the organic cationic surfactant and/or the siloxane cationic surfactant (B).
• divalent linking group D 2 comprises, alternatively is a linear or branched alkyl and/or alkylene group.
• divalent linking group D 2 comprises, alternatively is, a C 1 -C 18 hydrocarbon moiety, such as the linear hydrocarbon moiety having the formula -(CH 2 ) d -, defined above with respect to D 1 (i.e., where subscript d is from 1 to 18).
• subscript d is from 1 to 16, such as from 1 to 12, alternatively from 1 to 10, alternatively from 1 to 8, alternatively from 1 to 6, alternatively from 2 to 6, alternatively from 2 to 4.
• subscript d is 3, such that divalent linking group D 2 comprises a propylene (i.e., a chain of 3 carbon atoms).
• each alkyl and/or alkylene group suitable for D 2 may independently be unsubstituted and unbranched, or substituted and/or branched.
• divalent linking group D 2 comprises, alternatively is, an unsubstituted alkylene group.
• divalent linking group D 2 comprises, alternatively is, a substituted hydrocarbon group, such as a substituted alkylene group.
• divalent linking group D 2 typically comprises a carbon backbone having at least 2 carbon atoms and at least one heteroatom (e.g. O, N, S, etc.), such that the backbone comprises an ether moiety, amine moiety, etc.
• divalent linking group D 2 comprises, alternatively is, an amino substituted hydrocarbon group (i.e., a hydrocarbon comprising a nitrogen-substituted carbon chain/backbone).
• the divalent linking group D 2 is an amino substituted hydrocarbon having formula –D 4 -N(R 8 )-D 4 -, such that the organic cationic surfactant may be represented by the following formula: where each D 4 is an independently selected divalent linking group, R 8 is Y or H, and each Z 2 , Y, R, subscript b, X, superscript y, superscript x, and subscript n is as defined and described above.
• each D 4 of the amino substituted hydrocarbon divalent linking group is independently selected.
• each D 4 comprises an independently selected alkylene group, such as any of those described above with respect to divalent linking group D 3 of the siloxane cationic surfactant (B).
• each D 4 is independently selected from alkylene groups having from 1 to 8 carbon atoms, such as from 2 to 8, alternatively from 2 to 6, alternatively from 2 to 4 carbon atoms.
• each D 4 is propylene (i.e., -(CH 2 ) 3 -).
• D 4 may be, or comprise, another divalent linking group (i.e., aside from the alkylene groups described above). Moreover, each D 4 may be substituted or unsubstituted, linear or branched, and various combinations thereof.
• R 8 of the amino substituted hydrocarbon is H or quaternary ammonium moiety Y (i.e., of formula -D-NR 1 3 + , as set forth above).
• R 8 H such that the organic cationic surfactant may be represented by the following formula: where each Z 2 , D 4 , Y, R, subscript b, X, superscript y, superscript x, and subscript n is as defined and described above.
• superscript y is 1 or 2, controlled by subscript b. More particularly, the number of quaternary ammonium moieties Y will be controlled by subscript b as 1 or 2, providing a total cationic charge of +1 or +2, respectively.
• superscript x will also be 1 or 2, such that the organic cationic surfactant will be charge balanced.
• superscript x will be 1, 2, or 3, such that the organic cationic surfactant will be charge balanced.
• subscript b is 1 and X is monoanionic, such that the organic cationic surfactant has the following formula: , where each Z 2 , D 4 , R, R 1 , and X is as defined and described above.
• D 2 is the covalent bond
• Z 2 is the linear alkyl group
• subscript b is 1
• R is H
• each linking group D is a (2-hydroxy)propylene group
• each R 1 is methyl
• X is a monoanion, such that the organic cationic surfactant has the following formula: , where subscript f is from 5 to 17 (e.g. from 5 to 11, alternatively from 5 to 9), and X is as defined and described above.
• Z 2 is a linear alkyl group having from 3 to 13 carbon atoms
• D 2 the divalent linking group and the divalent linking group D 2 is the amino substituted hydrocarbon where each D 4 is propylene and R 8 is H, subscript b is 1, R is H, each linking group D is a (2-hydroxy)propylene group, each R 1 is methyl, and X is a monoanion, such that the organic cationic surfactant has the following formula: where subscript f and X are as defined and described above.
• the organic cationic surfactant is configured the same as described immediately above, but with R 8 being the quaternary ammonium moiety Y, such that the organic cationic surfactant has the following formula: where subscript f and each X are as defined and described above.
• each anion X of the organic cationic surfactant is an inorganic anion having one to three valences.
• examples of such anions include monoanions such as chlorine, bromine, iodine, aryl sulfonates having six to 18 carbon atoms, nitrates, nitrites, and borate anions, dianions such as sulfate and sulfite, and trianions such as phosphate.
• each X is a halide anion. In some such embodiments, each X is chloride (i.e., Cl- ).
• the stability enhancer (C) comprises a cationic moiety or is cationic
• another specific example of the stability enhancer (C) is an organic cationic surfactant, i.e., a complex comprising a cationic nitrogen-containing compound charge balanced with a counter ion.
• the organic cationic surfactant can comprise several substituted or unsubstituted hydrocarbon moieties.
• the stability enhancer (C) has the general formula (III): wherein Z 2 is as described; D 2 is as described above; subscript c is 0, 1, 2, 3, or 4; and each R, superscript y, X, subscript n, and superscript x is independently selected and as defined above. [0084] With regard to general formula (III), each R, superscript y, X, subscript n, and superscript x is independently selected and as defined above with respect to the siloxane cationic surfactant (B) and general formula (II) of component (C).
• the stability enhancer (C) comprises a cationic surfactant other than or in addition to the organic cationic surfactant described above.
• cationic surfactants include various fatty acid amines and amides and their derivatives, and the salts of the fatty acid amines and amides.
• aliphatic fatty acid amines examples include dodecylamine acetate, octadecylamine acetate, and acetates of the amines of tallow fatty acids, homologues of aromatic amines having fatty acids such as dodecylanalin, fatty amides derived from aliphatic diamines such as undecylimidazoline, fatty amides derived from aliphatic diamines such asundecylimidazoline, fatty amides derived from disubstituted amines such as oleylaminodiethylamine, derivatives of ethylene diamine, quaternary ammonium compounds and their salts which are exemplified by tallow trimethyl ammonium chloride, dioctadecyldimethyl ammonium chloride, didodecyldimethyl ammonium chloride, dihexadecyl ammonium chloride, alkyltrimethylammonium
• component (C) may comprise a quaternary ammonium salt, such as N-octylrimethylammonium chloride.
• the stability enhancer (C) comprises, alternatively is, a nonionic surfactant.
• nonionic surfactants include polyoxyethylene alkyl ethers (such as, lauryl, cetyl, stearyl or octyl), polyoxyethylene alkylphenol ethers, polyoxyethylene lauryl ethers, polyoxyethylene sorbitan monoleates, polyoxyethylene alkyl esters, polyoxyethylene sorbitan alkyl esters, polyethylene glycol, polypropylene glycol, diethylene glycol, ethoxylated trimethylnonanols, polyoxyalkylene glycol modified polysiloxane surfactants, polyoxyalkylene- substituted silicones (rake or ABn types), silicone alkanolamides, silicone esters, silicone glycosides, dimethicone copolyols, fatty acid esters of polyols, for instance sorbitol and glyceryl mono-, di-, tri- and sesqui- oleates and stearates, glyceryl and polyethylene glycol laurates;
• the stability enhancer (C) may be formed in situ in the composition.
• the stability enhancer (C) may be formed in situ by protonating an amine via an acid buffer or solution in the composition, resulting in a cationic species.
• the amine may be a tertiary amine (e.g. N,N-diemthylhexylamine, N,N-dimethyloctylamine, and/or N,N- dimethyldecylamine)
• the acid buffer may be hydrochloric acid.
• the amine includes an alkyl group having at least 4, alternatively at least 5, alternatively at least 6, carbon atoms such that the cationic species formed in situ is amphiphilic.
• the stability enhancer (C) surfactant may comprise a combination or two or more different compounds that differ in at least one property such as structure, molecular weight, degree of branching, silicon and/or carbon content, number of cationic quaternary ammonium groups, etc.
• the stability enhancer (C), when utilized, may be utilized in any amount in the composition, depending on the form of the composition prepared, a desired use thereof, other components present therein, etc.
• the stability enhancer (C) when the composition is formulated as a concentrate, the stability enhancer (C) will be present in higher relative amounts as compared to non-concentrated forms (e.g. aqueous foam compositions). As such, the stability enhancer (C) may be present in the composition in any amount, such as an amount of from 0 to 60 wt.%, based on the total weight of the composition (i.e., wt./wt.).
• the composition comprises the stability enhancer (C) in an amount to provide a weight ratio of the stability enhancer (C) to the siloxane cationic surfactant (B) of from greater than 0:1: to 10:1 (C)/(B).
• a weight ratio of the stability enhancer (C) to the siloxane cationic surfactant (B) of from greater than 0:1: to 10:1 (C)/(B).
• each of the siloxane cationic surfactant (B) and the organic cationic surfactant described above are independently selected when the organic cationic surfactant is utilized, and thus each variable in formulas (I) and (II), even where representing the same group/moiety and/or having the same definition, is independently selected.
• the composition may comprise (D) a carrier vehicle (e.g.
• the carrier vehicle (D) will be selected based on the particular components (A) and (B) selected, as well as any other components utilized in the composition and/or to be combined with the composition (i.e., in an end-use composition).
• Carrier vehicles are known in the art, and generally comprise solvents, fluids, oils, and the like, as well as combinations thereof.
• the carrier vehicle (D) may facilitate introduction of certain components into the composition, mixing and/or homogenization of the components, etc.
• the particular carrier vehicle (D) will be selected based on the solubility of components (A) and (B) and/or other components utilized in the composition, the volatility (i.e., vapor pressure) of the solvent, the end-use of the composition, etc.
• the solubility refers to the carrier vehicle (D) being sufficient to dissolve and/or disperse components (A) and (B) to form a homogenous composition.
• solvents for use in the composition may generally be selected for fluidizing and/or dissolving components (A) and (B), or another component of the composition.
• organic solvents may be utilized in the composition, such organic solvents will typically be removed before utilizing the composition, or an end-use composition comprising the same, especially if the organic solvents are flammable.
• solvents include aqueous solvents, organic solvents, and combinations thereof.
• aqueous solvents include water and polar and/or charged (i.e., ionic) solvents compatible with water.
• organic solvents include those comprising an alcohol, such as methanol, ethanol, isopropanol, butanol, and n-propanol; a ketone, such as acetone, methylethyl ketone, and methyl isobutyl ketone; an aromatic hydrocarbon, such as benzene, toluene, and xylene; an aliphatic hydrocarbon, such as heptane, hexane, and octane; a glycol ether, such as propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol n-butyl ether, propylene glycol n-propyl ether, and ethylene glycol n-butyl ether; a halogenated hydrocarbon, such as dichloromethane, 1,1,1-trichloroethane, and chloroform; dimethyl sulfoxide; dimethyl formamide, acetonitrile
• polar organic solvents generally compatible with water include methanol, ethanol, 1-propanol, 2-propanol, 2-methyl-2-propanol, 2-butanone, tetrahydrofuran, acetone, and combinations thereof.
• fluids include organic fluids, silicone fluids, and combinations thereof.
• Organic fluids typically comprise an organic oil including a volatile and/or semi-volatile hydrocarbon, ester, and/or ether.
• volatile hydrocarbon oils such as C 6 -C 16 alkanes, C 8 -C 16 isoalkanes (e.g.
• organic fluids include aromatic hydrocarbons, aliphatic hydrocarbons, alcohols having more than 3 carbon atoms, aldehydes, ketones, amines, esters, ethers, glycols, glycol ethers, alkyl halides, aromatic halides, and combinations thereof.
• Hydrocarbons include isododecane, isohexadecane, Isopar L (C 11 -C 13 ), Isopar H (C 11 -C 12 ), hydrogentated polydecene.
• Ethers and esters include isodecyl neopentanoate, neopentylglycol heptanoate, glycol distearate, dicaprylyl carbonate, diethylhexyl carbonate, propylene glycol n- butyl ether, ethyl-3 ethoxypropionate, propylene glycol methyl ether acetate, tridecyl neopentanoate, propylene glycol methylether acetate (PGMEA), propylene glycol methylether (PGME), octyldodecyl neopentanoate, diisobutyl adipate, diisopropyl adipate, propylene
• Silicone fluids typically comprise a low viscosity and/or volatile siloxane.
• silicone fluids include those including a low viscosity organopolysiloxane, a volatile methyl siloxane, a volatile ethyl siloxane, a volatile methyl ethyl siloxane, or the like, or combinations thereof.
• silicone fluids typically have a viscosity at 25 °C in the range of 1 to 1,000 mm 2 /sec.
• silicone fluids include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, tetradecamethylhexasiloxane, hexadeamethylheptasiloxane, heptamethyl-3- ⁇ (trimethylsilyl)oxy) ⁇ trisiloxane, hexamethyl-3,3, bis ⁇ (trimethylsilyl)oxy ⁇ trisiloxane pentamethyl ⁇ (trimethylsilyl)oxy ⁇ cyclotrisiloxane as well as polydimethylsiloxanes, polyethylsiloxanes, polymethylethylsiloxanes, polymethylphenylsiloxanes, polydiphen
• silicone fluids include polyorganosiloxanes with vapor pressures of from 5 x 10 -7 to 1.5 x 10 -6 m 2 /s.
• Other carrier vehicles may also be utilized.
• the carrier vehicle comprises an ionic liquid.
• ionic liquids include anion-cation combinations.
• the anion is selected from alkyl sulfate-based anions, tosylate anions, sulfonate-based anions, bis(trifluoromethanesulfonyl)imide anions, bis(fluorosulfonyl)imide anions, hexafluorophosphate anions, tetrafluoroborate anions, and the like
• the cation is selected from imidazolium-based cations, pyrrolidinium-based cations, pyridinium-based cations, lithium cation, and the like.
• combinations of multiple cations and anions may also be utilized.
• the ionic liquids typically include 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1-methyl-1-propylpyrrolidinium bis- (trifluoromethanesulfonyl)imide, 3-methyl-1-propylpyridinium bis(trifluoromethanesulfonyl)imide, N-butyl-3-methylpyridinium bis(trifluoromethanesulfonyl)imide, 1-methyl-1-propylpyridinium bis(trifluoromethanesulfonyl)imide, diallyldimethylammonium bis(trifluoromethanesulfonyl)imide, methyltrioctylammonium bis(trifluoromethanesulfonyl)imide, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1,2-dimethyl-3-propyl
• the carrier vehicle (D) is an aqueous solvent, and comprises, alternatively consists essentially of, alternatively is, water.
• the water is not particularly limited.
• purified water such as distilled water and ion exchanged water, saline, a phosphoric acid buffer aqueous solution, and the like, or combinations and/or modifications thereof, can be used.
• the carrier vehicle (D) comprises water and at least one other solvent (i.e., a co-solvent), such as a water-miscible solvent. Examples of such co-solvents may include any of the water miscible carrier vehicles described above.
• co- solvents include glycerol, sorbitol, ethylene glycol, propylene glycol, hexylene glycol, polyethylene glycol (PEG), ethers of diethylene and dipropylene glycols (e.g. methyl, ethyl, propyl, and butyl ethers, etc.), and the like, as well as derivatives, modifications, and combinations thereof.
• the amount of carrier vehicle (D) utilized is not limited, and depend on various factors, including the type of solvent selected, the amount and type of components (A) and (B) employed, the form of the composition (i.e., whether a concentrate, intermediate, or end-use composition), etc.
• the amount of carrier vehicle (D) utilized may range from 0.1 to 99.9 wt.%, based on the total weight of the composition, or the total combined weights of components (A), (B), and (C) (if utilized).
• the carrier vehicle (D) is utilized in an amount of from 50 to 99.9 wt.%, such as from 60 to 99.9, alternatively of from 70 to 99.9, alternatively of from 80 to 99.9, alternatively of 90 to 99.9, alternatively of from 95 to 99.9, alternatively of from 98 to 99.9, alternatively of from 98.5 to 99.9, alternatively of from 98.5 to 99.7, alternatively of from 98.7 to 99.7 wt.%, based on the combined weights of components (A), (B), and optionally (C).
• a weight ratio of water to component (A) is from 90:1 to 600:1.
• the anionic polymer (A) and the siloxane cationic surfactant (B) may be used alone (i.e., neat or in combination with the carrier vehicle (D)), together with at least one auxiliary component, or as an auxiliary to at least one other component, optionally in the presence of one of more additives (e.g. agents, adjuvants, ingredients, modifiers, etc.).
• the composition further comprises one or more additional components, such as one or more additives.
• additives may be classified under different terms of art and just because an additive is classified under such a term does not mean that it is thusly limited to that function.
• some of these additives may be present in a particular component of the composition, or instead may be incorporated when forming the composition.
• the composition may comprise any number of additives, e.g. depending on the particular type and/or function of the same in the composition.
• the composition may comprise one or more additive components comprising, alternatively consisting essentially of, alternatively consisting of: (E) a rheology modifier; (F) a pH control agent; and (G) a foam enhancer.
• the composition further comprises the rheology modifier (E).
• the rheology modifier (E) is not particularly limited, and is generally selected to alter the viscosity, flow property, and/or a foaming property (i.e., foam-forming ability and/or foam stability) of the composition, or an end-use composition comprising the same.
• the rheology modifier (E) is not particular limited, and may comprise a thickener, stabilizer, viscosity modifier, thixotropic agent, etc., or combinations thereof, which will be generally selected from natural or synthetic thickening compounds.
• the rheology modifier (E) comprises one or more water soluble and/or water compatible thickening compounds (e.g. water-soluble organic polymers, etc.). If utilized, the rheology modifier (E) is different from the anionic polymer (A).
• Examples of compounds suitable for use in or as the rheology modifier (E) include acrylamide copolymers, acrylate copolymers and salts thereof (e.g.
• sodium polyacrylates etc.
• celluloses e.g. methylcelluloses, methylhydroxypropylcelluloses, hydroxyethylcelluloses, hydroxypropylcelluloses, polypropylhydroxyethylcelluloses, carboxymethylcelluloses, etc.
• starches e.g. starch, hydroxyethylstarch, etc.
• polyoxyalkylenes e.g. PEG, PPG, PEG/PPG copolymers, etc.
• carbomers e.g. sodium alginate
• various gums e.g.
• arabic gums cassia gums, carob gums, scleroglucan gums, xanthan gums, gellan gums, rhamsan gums, karaya gums, carrageenan gums, guar gums, etc.
• cocamide derivatives e.g. cocamidopropyl betaines, etc.
• medium to long-chain alkyl and/or fatty alcohols e.g. cetearyl alcohol, stearyl alcohol, etc.
• gelatin e.g. fructose, glucose, PEG-120 methyl glucose diolate, etc.
• the composition comprises the pH control agent (F).
• the pH control agent (F) is not particular limited, and may comprise or be any compound suitable for modifying or adjusting the pH of the composition and/or maintaining (e.g. regulating) the pH of the composition in a particular range.
• the pH control agent (F) comprises, alternatively is a pH modifier (e.g. an acid and/or a base), a pH buffer, or a combination thereof, such as any one or more of those described below.
• acids generally include mineral acids (e.g. hydrochloric acid, phosphoric acid, sulfuric acid, etc.), organic acids (e.g.
• the pH control agent (F) comprises, alternatively is, the pH buffer.
• Suitable pH buffers are not particularly limited, and may comprise, alternatively may be, any buffering compound capable of adjusting the pH of the composition and/or maintaining (e.g. regulating) the pH of the composition in a particular range.
• suitable buffers and buffering compounds may overlap with certain pH modifiers, including those described above, due to the overlap in functions between the additives.
• the pH buffer and the pH modifier may be independently or collectively selected in view of each other.
• suitable pH buffers are selected from buffering compounds that include an acid, a base, or a salt (e.g. comprising the conjugate base/acid of an acid/base).
• buffering compounds generally include alkali metal hydroxides (e.g. sodium hydroxide, potassium hydroxide, etc.), carbonates (e.g.
• ком ⁇ онентs include citrate buffers, glycerol buffers, borate buffers, phosphate buffers, and combinations thereof (e.g. citric acid-phosphate buffers, etc.).
• buffering compounds suitable for use in or as the pH buffer of the pH control agent (F) include ethylenediaminetetraacetic acids (e.g. disodium EDTA, etc.), triethanolamines (e.g.
• the composition comprises the foam enhancer (G).
• Particular compounds/compositions suitable for use in or as the foam enhancer (G) are not limited, and generally include those capable of imparting, enhancing, and or modifying a foaming property (e.g. foamability, foam stability, foam drainage, foam spreadability, foam density, etc.) of the composition, or an end-use composition comprising the same.
• the foam enhancer (G) comprises a stabilizing agent selected from electrolytes (e.g. alkali metal and/or alkaline earth salts of various anions, such as chloride, borate, citrate, and/or sulfate salts of sodium, potassium, calcium, and/or magnesium, aluminum chlorohydrates, etc.), polyelectrolytes (e.g.
• electrolytes e.g. alkali metal and/or alkaline earth salts of various anions, such as chloride, borate, citrate, and/or sulfate salts of sodium, potassium, calcium, and/or magnesium, aluminum chlorohydrates, etc.
• polyelectrolytes e.g.
• hyaluronic acid salts such as sodium hyaluronates, etc.
• polyols e.g. glycerine, propylene glycols, butylene glycols, sorbitols
• hydrocolloids and the like, as well as derivatives, modifications, and combinations thereof.
• foam enhancers suitable for use in or as the foam enhancer (G) are known in the art.
• the foam enhancer (G) may comprise a polymeric stabilizer, such as those comprising a polyacrylic acid salt, a modified starch, a partially hydrolyzed protein, a polyethyleneimine, a polyvinyl resin, a polyvinyl alcohol, a polyacrylamids, a carboxyvinyl polymer, or combinations thereof.
• the foam enhancer (G) may comprise a thickener, such as those comprising one or more gums (e.g. xanthan gum), collagen, galactomannans, starches, starch derivatives and/or hydrolysates, cellulose derivatives (e.g.
• the composition may comprise one or more additional components/additives, i.e., other than those described above, which are known in the art and will be selected based on the particular components utilized in the composition and a desired end-use thereof.
• the composition may comprise: a filler; a filler treating agent; a surface modifier; a binder; a compatibilizer; a colorant (e.g. a pigment, dye, etc.); an anti-aging additive; a flame retardant; a corrosion inhibitor; a UV absorber; an anti-oxidant; a light-stabilizer; a heat stabilizer; and the like, as well as derivatives, modifications, and combinations thereof.
• the composition may be prepared by combining components (A) and (B), as well as any optional components (e.g. components (C)-(G) described above), in any order of addition, optionally with a master batch, and optionally under mixing.
• the composition is prepared by pre-mixing component (A) with water to prepare an intermediate composition that is subsequently combined with component (B) to prepare the composition.
• the composition is prepared by pre-mixing component (B) with an optional component to prepare an intermediate composition that is subsequently combined with component (A) to prepare the composition.
• component (B) is combined with the pH control agent (F) to prepare a siloxane cationic surfactant composition, which is subsequently combined with component (B) to prepare the composition.
• the pH control agent (F) is a mineral acid (e.g.
• the pH control agent (F) may comprise multiple functions, such as to adjust the pH of one or more individual components of the composition, to buffer one or more intermediate compositions, and/or to modify, control, and/or buffer the pH of the composition by itself or in combination with one or more other components.
• the composition may be prepared as a concentrate, e.g. via combining components (A) and (B), optionally together with any of components (C)-(G).
• the composition when formulated for dilution, may comprise a predominate amount of component (D) (e.g. >50, alternatively >75, alternatively >90 wt.%, based on the total weight of the composition), and still be defined as a concentrate.
• the foam stabilizing composition may be formulated as a foam-forming composition (e.g. via diluting a concentrated of the composition, as described above) or utilized as an additive to prepare a foam-forming composition (e.g. via combining the foam stabilizing composition with a base formulation, i.e., a formulation comprising foaming agents, solvents/carriers, additives, etc.).
• the foaming composition can be prepared by providing water (e.g.
• the foam-forming composition comprising the foam stabilizing composition once prepared, may be aerated or otherwise expanded (e.g. via foaming equipment, application to an aerated water stream/flow, etc.) to form a foam composition (i.e., a “foam”).
• the foam prepared with the foam stabilizing composition is suitable for use in various applications.
• the composition may be utilized in an aqueous foam, or similar such foam, which may be utilized in extinguishing, suppressing, and/or preventing fire.
• foams prepared therewith may be used for extinguishing fires involving chemicals with low boiling points, high vapor pressures, and/or limited aqueous solubility (e.g. gasoline, organic solvents, etc.), which are typically extremely flammable and/or difficult to maintain/extinguish.
• a fire may be extinguished by contacting the fire with foam (e.g. by spraying the foam onto the fire, spraying the foam-forming composition over the fire to prepare the foam thereon, etc.).
• the foam may be utilized to secure chemicals (e.g. from a spill or leak thereof) to limit vapor leak and/or ignition, by the applying the foam to the top of the spill/leak, or otherwise forming the foam thereon.
• chemicals e.g. from a spill or leak thereof
• the foam may be utilized to secure chemicals (e.g. from a spill or leak thereof) to limit vapor leak and/or ignition, by the applying the foam to the top of the spill/leak, or otherwise forming the foam thereon.
• Table 1 Components Utilized [00 0] epaato a pe epaato o S o a e Cato c Su acta t ( ) [00121] 3-aminopropyltris(trimethylsiloxy)silane (601.64 g), Solvent 2 (434.55 g), and Acid Solution 2 (1.25 g) were disposed and mixed in a 2L glass reactor. The contents of the reactor were stirred and heated to 60 °C. Then glycidyltrimethylammonium chloride (381.4 g; 72.7% solution in water) was metered into the reactor over 30 minutes.
• Preparation Example 3 Preparation of Stability Enhancer (C1) [00125] 1-hexylamine (391.99 g) and Solvent 2 (227.46 g) were disposed and mixed in a 2L glass reactor. The contents of the reactor were stirred and heated to 60 °C. Then glycidyltrimethylammonium chloride (854.57 g; 72.7% solution in water) was metered into the reactor over 30 minutes. The contents of the reactor were held at 60 °C for 3-3.5 hours, after which the heat was removed, and Acid Solution 2 (225.94 g) was added once the contents of the reactor were cooled to 30 °C.
• Acid Solution 2 225.94 g
• Examples 1-29 and Comparative Examples 1-10 Foam stabilizing compositions were prepared for Examples 1-29 and Comparative Examples 1-10. Tables 2-6 below detail the components and amounts utilized in each of the foam stabilizing compositions of Examples 1-29 and Comparative Examples 1-10. The values in Tables 2-6 are in wt.% based on the total weight of each particular foam stabilizing composition. The Wt. Ratio (A)/(B) ratio in each of Tables 2-6 is a weight basis.
• the Molar Ratio (A)/(B) in Tables 2-4 and 6 is based on the number of moles of ionic groups in component (A) to the number of moles of ionic groups in component (B).
• C.E. in Table 6 indicates Comparative Example.
• the foam stabilizing compositions of Examples 1-29 and Comparative Examples 1-10 were prepared by first dispersing the particular Anionic Polymer (A) into Solvent 1, if utilized, to give a slurry. Then, Diluent is combined with the slurry until the Polymer (A) is solubilized in Diluent to give a solution.
• Foam Stability Test Procedure [00134] Parker Eight 10 oz handhold foaming soap dispenses were used to generate foams with the foam stabilizing compositions of Examples 1-29 and Comparative Examples 1-10. A flat- bottom crystallizing dish with a diameter of 100 mm and height of 50 mm was used to contain heptane. A digital camera (Canon Rebel T3i) with an 18-55 mm lens was used to capture images of the foams from the side of the dish at fixed time intervals to visualize the dynamics of foam collapse. The light source, focus, aperture, and shutter speed were adjusted manually according to needs.40 mL of heptane was first poured into the dish.
• the dish was heated on a hot plate to allow heptane to reach 60 °C and maintained at that temperature. Then, 100 mL of foam formed with each of the foam stabilizing compositions of Examples 1-29 and Comparative Examples 1- 10 was dispensed on top of the hot heptane. The hot plate was subsequently switched off and a timer was started. The timer was stopped when a hole formed in the foam blanket which exposed the heptane underneath. The foam stability time was recorded. [00135] Table 7-9 below detail the foam stability time associated with the foams formed with the foam stabilizing compositions of Examples 1-29 and Comparative Examples 1-10 in accordance with the foam stability test procedure described above.
• the constant foam flow rate was achieved by maintaining constant air flow and by a liquid leveling system that continuously transferred additional foam stabilizing composition from a leveling vessel to a foam generation vessel. This liquid level was maintained at 3 cm above a sparger disc.
• Extinction experiments consisted of a pre-burn of the heptane pool for 60 s followed by the foam application at a constant flow rate until fire extinguishment, which is measured as extinction time as a function of flow rate. If when no extinction event was observed at low foam flow rates, foam flow was turned off after 180 s to prevent overflow of the foam. As the foam drained liquid into the fuel, fuel overflow from an extinction vessel was prevented by lowering a tygon tube connected to the bottom of the extinction vessel to a specified height.
• Tables 11 and 13 show the extinction times for foams formed with Examples 1 and 2 and Comparative Examples 2 and 3 for gasoline and heptane, respectively, as measured in accordance with the Pool Test General Procedure.
• the data from Table 11 is included herewith as Figure 1, and the data from Table 13 is included herewith as Figure 2.
• the collection vessel has a 0.25 inch orifice at its base that was fit with a brass barbed hose fitting for 0.25 inch ID hose (McMaster-Carr, Catalog number 5346K42).
• a needle valve was attached to the opposite end of the Tygon tubing with ⁇ 40 mm of tubing in between the hose fitting and the needle valve. After priming the nozzle, foam was sprayed onto the foam slider so that it would flow into the collection vessel (the needle valve was closed during foam collection). When the foam reached the top of the collection vessel, a stopwatch was started to track the age of the foam for subsequent drainage time evaluation.
• the expansion ratio of a foam is the ratio of foam volume to the volume of liquid foam solution. Assuming the liquid foam solution has a density similar to water and approximating it as 1 g/mL, the volume of the liquid foam solution can be approximated by the mass of the foam.
• the expression for the expansion ratio is Where V f is the foam volume, V liq is the volume of the liquid solution in the foam, and m f is the mass of the foam.
• the expansion ratio was calculated by dividing the volume of foam (1600 mL) by the mass of foam according to Equation above using three different methods: (1) graduated cylinder method, (2) nozzle to jar collection method, and (3) ratio of drainage rates.
• Drainage Time [00151] Drainage time measurements were based on UL 162 and EN 1568 standards. In particular, with the needle valve closed, the collection vessel was filled with foam using the foam slider as described above (see Foam Collection). When the foam reached the top of the vessel, a stopwatch was started and the outside of the vessel was wiped clean using paper towels. After weighing the vessel for the expansion ratio calculation, the vessel was clamped to a ring stand and positioned over a 500 mL glass graduated cylinder.
• the graduated cylinder was on a balance connected to a computer to automatically record mass as a function of time. Before starting the drainage experiment, the graduated cylinder was tared on the balance. [00152] To measure the drainage time of the foam, the needle valve was slowly opened at the same time that the balance began recording mass (1 measurement every 2 seconds). The time of the stopwatch was also recorded to later correct the times recorded by the computer to reflect the age of the foam. The needle valve was only opened enough so that liquid (not foam) was able to drain into the graduated cylinder as it drained from the foam. [00153] A camera (Canon EOS Rebel T3i) was set up on a tripod to image the graduated cylinder. A piece of black poster board was positioned behind the graduated cylinder.
• the camera was connected to a computer and controlled remotely using the Canon EOS Utility software.
• the mass drained was plotted as a function of foam age. A short script was written in MATLAB to identify the time at which the mass collected first exceeded 25% of the mass of the foam in the collection vessel at the start of the experiment; it was recorded as the 25% drain time. Because the 25% drain time is reported to the nearest minute, small errors associated with starting the stopwatch and syncing the stopwatch to the computer recording start time are insignificant.
• MILSPEC MIL-F-24385 Test [00156] Six foot diameter pool fire tests outlined in MIL-F-24385 were performed. However, the same test was carried out with gasoline, heptane, and Jet A fuel as the fuel.
• Passing or failure of the torch test was defined by the presence of sustained flames 30 seconds after waving the torch over the surface of the foam blanket.
• the burnback test occurred 10 minutes after stopping foam application in the pan. This test involved inserting a 12-inch diameter steel cylinder (approximately 18 inches long) into the pan and manually removing the foam within the pipe using a ladle. At the designated time, the torch was used to reignite the fuel within the cylinder. The fire was allowed to burn for 1 minute before the pipe was lifted straight up and out of the pan and set aside. The fire was observed for 5 minutes or until extinguishment. A pass as defined by the UL 162 standard is ⁇ 20% area of the pan reignited after 5 minutes.
• Table 15 below shows the results of the UL 162 Type II Test for Example 1 and Comparative Example 2.
• Figures 1 and 2 show that Examples 1 and 2 extinguish gasoline and heptane fires much faster than Comparative Example 2 (which does not include component (A)) at all the foam flow rates tested.
• the extinction time of Examples 1 and 2 is even shorter than the extinction time of fluorine containing Comparative Example 1 at foam flow rates less than 200 mL/min for both gasoline and heptane.
• Comparative examples 2, 5, 6, 7, 8, and 9 in Table 10 show that in the absence of any one or more of components (A) and (B), foam stability is much lower as compared to that of the Examples.

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