WO2012105903A1 - Composition and method for fire control - Google Patents

Composition and method for fire control Download PDF

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Publication number
WO2012105903A1
WO2012105903A1 PCT/SE2012/050101 SE2012050101W WO2012105903A1 WO 2012105903 A1 WO2012105903 A1 WO 2012105903A1 SE 2012050101 W SE2012050101 W SE 2012050101W WO 2012105903 A1 WO2012105903 A1 WO 2012105903A1
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WO
WIPO (PCT)
Prior art keywords
composition
fire
composition according
containing compound
phosphorous containing
Prior art date
Application number
PCT/SE2012/050101
Other languages
French (fr)
Inventor
Freddy Kai Klaffmo
Original Assignee
Hygienic Interior Treatment Sweden Ab
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Publication of WO2012105903A1 publication Critical patent/WO2012105903A1/en

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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
    • A62D1/0028—Liquid extinguishing substances
    • A62D1/0035—Aqueous solutions
    • 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
    • A62D1/0064—Gels; Film-forming compositions
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/06—Organic materials
    • C09K21/12—Organic materials containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/14—Macromolecular materials
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/44—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen containing nitrogen and phosphorus
    • D06M13/447—Phosphonates or phosphinates containing nitrogen atoms

Definitions

  • the present invention relates to a composition for use in fire control applications, for fire extinguishing and as flame retardant.
  • Two general principles for the repression of the harm and seriousness of burning combustible materials include: (i) the lowering of the materials tendency to kindle by treatment with a suitable composition, e.g. impregnation with a flame retardant, and (ii) extinguishing of the fire with a suitable liquid, solid or gaseous composition.
  • suitable composition e.g. impregnation with a flame retardant
  • extinguishing of the fire with a suitable liquid, solid or gaseous composition.
  • compositions according to (i) include compositions containing e.g. organic phosphorous containing compounds, and according to (ii), e.g. bicarbonate, halogenated hydrocarbon and carbon dioxide containing compositions.
  • the composition has additional fire retarding properties in accordance with the first (i) general principle above.
  • the reason for this is to be found in the mechanisms by which a fire spreads and re-ignites.
  • a fire spreads by ignition of the material adjacent to the burning material either by direct contact with the flames or indirectly by the heat radiation.
  • the materials tendency to kindle is lowered by the fire-extinguishing composition, the spreading of the fire is inhibited and the extinguishing of the same facilitated.
  • the chances of subsequent re-ignition are diminished in comparison to the case of employment of fire- extinguishing means which are lacking additional fire retarding properties.
  • Additional desirable properties of a generally applicable fire-extinguishing composition, beside its effectiveness as flame retardant and fire extinguisher, include:
  • Suitable physicochemical properties e.g. viscosity, density and lipophilicity, to allow facile and controlled application by e.g. the spraying through nozzles and/or pumping through fire-hoses.
  • the most well known and used fire-extinguishing composition which fulfills many of the above mentioned desired properties, is common water.
  • water When used in fire- fighting, water contacts burning objects which results in sufficient cooling such that the burning objects fall below their combustion or ignition temperatures, and new ignition is precluded.
  • the water vaporizes to produce steam, which expands and expels the air necessary for combustion.
  • additives such as fire retarding chemicals, which may retard combustion for at least brief periods even after the water has evaporated, as well as having a direct fire-extinguishing effect, are being developed and are presently in use.
  • Additional additives include, for example, thickening agents and different foam forming agents.
  • Various forms of organic and inorganic phosphorous containing compounds represent commonly used fire retarding chemicals.
  • EP1065309 Al describes a composition for fire protection treatment of textile materials consisting of an aqueous solution of carbamide and a complex of the ammonium salt of an amidoalkylphosphonic acid and ammonium chloride.
  • the same or a similar composition can be obtained by dissolution of a commercially available product named Noflan®.
  • Noflan® a commercially available product named Noflan®.
  • a process for fireproofing treatment of textile materials by employment of this composition is also described.
  • the textile material which is first allowed to undergo an impregnation with a melamine-type resin and/or silicon-containing compounds in order to achieve e.g. a good fixation of the
  • this composition is subsequently treated with the composition, before heat treatment at elevated temperature.
  • One disadvantage of this composition is the multistep procedure utilized for the fireproofing treatment and e.g. the equipment needed for heating the material which is being fireproofed.
  • this composition is not well suited for storage over prolonged time periods due to physical and/or chemical change and decomposition, respectively.
  • EP1418178 Al discloses the ammonium salt of nitrilotris(methylene) triphosphonic acid amide, which is useful as a flame retardant of polymeric materials by addition to the polymer at the stage of polymer processing, and may be used for the fireproofing of e.g. textiles by treating the same with the corresponding aqueous formulation.
  • GB2299094 A discloses an aqueous formulation comprising a polymer in which an organic phosphorous containing compound has been bonded to the same. This formulation may be used for the fire proofing of e.g. textiles.
  • the organic phosphorous containing compounds, acting as starting materials to be bonded to suitable reactive functional groups of the polymer, include dialkyl phosphites, oligomers of
  • the material treated with the aqueous formulation e.g. a textile, is preferably subsequently treated at an elevated temperature in a drying oven in order to enhance the integrity of the polymer and/or complete the bonding of the organic phosphorous containing compound to the polymer.
  • composition such as e.g. an aqueous composition, according to the present invention, which comprises an organic phosphorous containing compound and a rheology modifier.
  • organic phosphorous containing compound is a compound of formula (I),
  • M is selected from the group consisting of H, H 4 , Na and K, and R is Ci- 6 alkyl or a substituent according to formula (II) (CH 2 )n
  • Q of the substituent according to formula (II) is independently selected from the group consisting of H, H 4 , Na and K, and n is an integer number from 1 to 3.
  • the composition according to the present invention may be used in fire control applications such as, for example, fire extinguishing of burning solid materials and for flame retardation of solid materials.
  • the disclosed composition essentially comprises an organic phosphorous containing compound and a rheology modifier, such as xhantan gum, and optionally at least one additional additive, such as a preservative.
  • a rheology modifier such as xhantan gum
  • the disclosed composition is preferably, but not necessarily, an aqueous composition, i.e. the main constituent, besides the organic phosphorous containing compound, the rheology modifier and the optional additive(s), is preferably but not necessarily water. Water is advantageous due to its low toxicity and its low cost etc. Other non-flammable main constituents are, however, potentially useful as solvents for the organic phosphorous containing compound, the rheology modifier and the optional additive(s) of the composition of the invention.
  • non-flammable main constituents include carbon dioxide, such as supercritical carbon dioxide, non-flammable halogenated hydrocarbons, such as polyfluorinated hydrocarbons, or any other non-flammable liquid, such as nonflammable liquids presently or previously used in fire-extinguishing applications, as well known by the skilled artisan.
  • the rheology modifier of the composition turns its viscosity to be dependent on shear rate and/or shear rate history.
  • the non-Newtonian, e.g. tixotropic or pseudoplastic, properties of the composition, in combination with the organic phosphorous containing compound, are highly beneficial in fire-control applications. For example, when the disclosed composition is pumped through e.g. a nozzle towards a burning material, it attains a fluid like form and is easily and well spread. When it has reached the burning material, or objects adjacent to the burning material, it attains a stable gel like form and the tendency of the composition to run off the same or to be blown away by the wind is minimized. Hence, a highly effective flame retardation of the adjacent objects is achieved, whereby the fire is effectively hindered from spreading while it is
  • the organic phosphorous containing compound may be a compound of formula (I) and complexes, e.g. the ammonium chloride complex, or solvates or hydrates thereof, or a commercially available product which contains at least one compound represented by formula (I) as a main constituent.
  • M may be selected from the group consisting of H, NH 4 , Na and K;
  • R may be Ci- 6 alkyl, e.g. methyl, ethyl, ⁇ -propyl and / ' -propyl, or a substituent according to formula (II).
  • n may be an integer number from 1 to 3, denoting the number of methylene- groups connected to each other to form a linkage between the nitrogen atom and the phosphorous atom.
  • composition according to the invention constitute an excellent fire fighting composition for solid materials, with fire extinguishing and fire retarding properties.
  • fire-extinguish or simply “extinguish” with reference to flames or fire, or the like, is to be understood herein a treatment which puts out the flames of a fire.
  • flame proofing or the like
  • fire proofing is to be understood herein a treatment which lowers a materials tendency to kindle, such as, for example, impregnation.
  • the inventor believes that the relatively low viscosity of the composition at the time it is pumped through e.g. a nozzle or the like, is causing the formation of small drops which are well spread towards the burning material and/or adjacent material which is not yet burning but face a risk of being ignited. When these drops adhere to the burning material or the adjacent material, they form a film with a relatively high viscosity. Due to the relatively high viscosity, the film is well adhered to the material without running off and thereby effective as a flame retardant for material adjacent to burning material.
  • the combination of the disclosed compositions fire extinguishing properties and the above described function as an effective flame retardant is advantageous in comparison to Newtonian fire extinguishing compositions of the prior art.
  • the composition may be used for the extinguishing of fires in combustible solid materials for which conventional fire fighting means are presently employed including, for example, wood (e.g. forest fires), paper, textile, plastic materials, rubber, such as in car tires, and industrial waste.
  • the composition may also be used for flame proofing of such combustible solid materials or other objects.
  • the composition may be sprayed towards objects, e.g. trees, houses, ships, airplanes or the like, which are adjacent to or near a fire to prevent the fire from spreading to these objects.
  • compositions in comparison to other flame retarding agents of the prior art with regard to fire fighting of burning solid materials, for example wood and tree-based materials, is its excellent flame retarding properties upon direct administration by e.g. spraying.
  • the suitable physicochemical properties of the composition for example its relatively low viscosity when sprayed but relatively high viscosity when adhered, enables an even spread of the composition on the surface of the solid material without running of the same. The close and long contact with the solid material then enables the phosphorous containing compound of the disclosed
  • composition to effectively penetrate and flame proof the material.
  • Examples of solid materials, of which the flames when burning may be extinguished with the composition of the invention include wood, trees, sawdust, paper, textile, house-refuse and industrial waste.
  • the herein mentioned solid materials may be flame proofed by treatment with the composition according to the invention.
  • the constituents of the composition according to the invention may be either commercially available products, available at a low cost, or easily prepared from cheap commercially available chemicals.
  • the composition according to the invention may be a solution or colloid with a homogenous appearance. It may be stable in respect of no, or minimal, observation of either of discoloration, precipitation, flocculation, creaming, breaking or coalescence when stored over relevant time-periods, e.g. over several months or a year at room temperature or 20 to 30°C. Thus, it is well suited for storage in e.g. tanks or containers, such as fire-extinguishers, in order to be readily available in case of a fire which needs to be extinguished.
  • such containers are made of a material that is not reacting chemically with the composition, for example, a suitable plastic material or stainless steel.
  • the relative proportions of the constituting ingredients, e.g the organic phosphorous containing compound and the rheology modifier, of the disclosed composition may be varied so that a composition which is optimal for the particular fire fighting or fire retarding application is obtained, as well known to the skilled person.
  • the physical properties, e.g. the viscosity may be fine-tuned by varying the relative proportions of the constituting ingredients to generate the desired drop-size and/or stream-shape as the composition is discharged through a particular nozzle, or other type of outlet, used in the application of the same.
  • the selection of the constituting ingredients within the scope of the invention may be chosen such that a composition which is optimal for the particular fire fighting or fire retarding application is obtained, as well known to the skilled person.
  • the combination of a particular organic phosphorous containing compound, rheology modifier and preservative may be chosen to optimize the stability of the composition so that no or minimal precipitation, or any other physical change, occurs upon storage of the composition in e.g. reservoirs at sites where readily available fire fighting capabilities are desired.
  • Another example include the addition of a suitable dyestuff to the composition for the fire-fighting of e.g. forest fires, whereby treated areas are easily spotted, as known in the art.
  • the composition may be used to pre-treat, by e.g. spraying, materials or objects in order to flame proof these.
  • materials and objects include, for example, houses located near a raging fire and trees located near a raging forest-fire.
  • the physicochemical properties of the composition which is making the composition facile to spread in an effective way, is advantageous in this application.
  • the rheology modifier of the composition may be selected from the group consisting of tixotropy enhancing or pseudoplasticity enhancing polysaccharides known in the art.
  • the rheology modifier may also be any other organic or inorganic compound as known in the art with a tixotropy enhancing or pseudoplasticity enhancing effect similar to the tixotropy enhancing or pseudoplasticity enhancing effect of a suitable polysaccharide, such as xanthan gum.
  • the rheology modifier of the composition may be xanthan gum. Advantages of xanthan gum include its readily availability, low cost and low toxicity.
  • the composition may comprise at least one preservative with e.g. antibacterial and antifungal effects to increase the long term storage capabilities of the composition at e.g. 20 to 30 °C to at least e.g. one year.
  • suitable preservatives include N-alkylisothiazolinones such as e.g. 2- methyl-2H-isothiazol-3-one, chlorinated N-alkylisothiazolinones such as e.g. 5-chloro- 2-methyl-2H-isothiazol-3-one, ethylparaben, benzalkonium chloride, 2-bromo-2- nitropropane-l,3-diol, or the like.
  • the composition may comprise 2-methyl-2H-isothiazol-3-one or 5-chloro-2-methyl-2H-isothiazol-3-one as
  • the composition may comprise a mixture of 2-methyl-2H-isothiazol-3-one and 5-chloro-2-methyl-2H-isothiazol-3-one, such as in commercially available Kathon CG® or as a mixture in the range from 1 :99 to 99: 1 by weight, respectively, as preservative.
  • the organic phosphorous containing compound may be commercially available Noflan®
  • the rheology modifier may be commercially available xanthan gum
  • the composition may additionally comprise 2-methyl-2H-isothiazol-3-one or 5-chloro-2-methyl-2H-isothiazol-3-one, or any mixture thereof, as preservative.
  • the organic phosphorous containing compound may be a compound of formula (I), or the ammonium chloride complex thereof, wherein R is methyl, ethyl, ⁇ -propyl or / ' -propyl, and M is H 4 ;
  • the rheology modifier may be commercially available xanthan gum; and the preservative may be 2-methyl-2H-isothiazol-3-one or 5-chloro-2-methyl-2H-isothiazol-3-one, or any mixture thereof.
  • composition comprising 1 to 30 % by weight of the organic phosphorous containing compound and 0.01 to 3 % by weight of the rheology modifier.
  • a composition comprising 5 to 25 % by weight of the organic phosphorous containing compound and 0.01 to 1 % by weight of the rheology modifier.
  • a composition comprising 0.01 to 0.5 %, such as 0.04 to 0.1 %, by weight of a preservative selected from the group consisting of 2-methyl-2H-isothiazol-3-one, 5-chloro-2-methyl-2H- isothiazol-3-one, and a mixture of 2-methyl-2H-isothiazol-3-one and 5-chloro-2- methyl-2H-isothiazol-3-one.
  • the organic phosphorous containing compound may be commercially available Noflan®.
  • the organic phosphorous containing compound may be the compound of formula (I).
  • the organic phosphorous containing compound may be the compound of formula (I), or the ammonium chloride complex thereof, wherein R is methyl, ethyl, ⁇ -propyl or / ' -propyl, and M is H 4 .
  • the organic phosphorous compound may be a compound of formula (I), wherein R is a substituent according to formula (II), M is H 4 , Q is H 4 , and n is 1.
  • the composition may be practically pH-neutral, i.e. its pH may be > 4, preferably > 6, and ⁇ 10, preferably ⁇ 8.
  • the pH of the composition may be adjusted accordingly with a suitable base, such as NaOH, or a suitable acid, such as HC1, or any other suitable base or acid as known in the art.
  • an additive of the composition of the present invention is a nitrogen containing compound.
  • nitrogen containing compounds are known in the art to act as fire retardants. Hence, such an additive has the advantage of further enhance the fire retarding properties of the composition according to the invention.
  • the organic phosphorous containing compound is the compound of formula (I), and an additive is a nitrogen containing compound.
  • the proportion of the nitrogen containing compound is in the range of 5 to 25 % by weight relative the compound of formula (I), preferably 8 to 12 %.
  • an additive of the composition of the present invention is urea.
  • the nitrogen containing additive of the composition is a fire retarding compound as known in the art, for example, a 1,3,5-triazine derivative, e.g. melamine; a heptazine derivative, e.g. melem and melon; and a cyanuric acid derivative, e.g tris-2-hydroxy ethyl isocyanurate.
  • a fire retarding compound as known in the art, for example, a 1,3,5-triazine derivative, e.g. melamine; a heptazine derivative, e.g. melem and melon; and a cyanuric acid derivative, e.g tris-2-hydroxy ethyl isocyanurate.
  • additional additives of the composition of the present invention comprise, for example, suitable magnesium-, aluminum-, zink-, and calcium salts, known in the art to have a fire retarding effect, including, for example, magnesium hydroxide, aluminum hydroxide, zinc
  • hydroxystannate calcium cyanamide, zinc cyanamide, boric acid, zinc borate and other boric acid salts.
  • One or several of these additives may further enhance the fire protecting properties of the composition according to the invention.
  • additional additives of the composition of the present invention comprise, for example, heat or light stabilizers, lubricants, film-forming agents, plasticizers, colorants, pigments, dyestuffs,
  • hydrophilizing agents may further enhance the stability, the fire fighting capability, the ease of spotting where the composition has been applied, and improve the physicochemical properties of the composition to be more optimal for the particular application.
  • the selection of a particular one of these additives for the enhancement or improvement of a given property, is known to the one skilled in the art.
  • an additional additive of the composition of the present invention may be a foam forming agent, as well known in the art, which results in the generation of, for example, an aqueous film forming foam, an alcohol-resistant aqueous film forming foam, and a film formed from fluoroproteins.
  • an additional additive of the composition of the present invention may be an anti-freeze agent such as ethylene- or propylene glycol.
  • the composition may then be stored at temperatures below freezing point, for example outdoors, without solidification.
  • the composition of the invention may be used as the main active fire fighting component in an active fire protection device.
  • an active fire protection device may be a hand held or cart-mounted fire extinguisher used to extinguish or control small fires.
  • a suitable propellant for example nitrogen, air, or carbon dioxide, may be used.
  • the composition may be used for fire extinguishing or fire retardation of fires of fire class A, according to the European or American classification system.
  • the composition may be used for fire control of a solid including, for example, wood, trees, sawdust, paper, textile, house-refuse, rubber, such as in car tires, and industrial waste.
  • the composition may comprise 5 to 25 % by weight of commercially available Noflan®, 0.01 to 1 % by weight of commercially available xanthan gum, and 0.04 to 0.1 %, by weight of a commercially available mixture of 2-methyl-2H-isothiazol-3-one and 5-chloro-2-methyl-2H- isothiazol-3-onem, such as an 1 :3 mixture.

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Abstract

The present invention discloses a composition comprising an organic phosphorous containing compound and a rheology modifier, for use in fire control applications. The fire control applications include fire extinguishing and flame proofing of solid materials.

Description

COMPOSITION AND METHOD FOR FIRE CONTROL TECHNICAL FIELD
The present invention relates to a composition for use in fire control applications, for fire extinguishing and as flame retardant.
BACKGROUND
Two general principles for the repression of the harm and seriousness of burning combustible materials include: (i) the lowering of the materials tendency to kindle by treatment with a suitable composition, e.g. impregnation with a flame retardant, and (ii) extinguishing of the fire with a suitable liquid, solid or gaseous composition. Examples of compositions according to (i) include compositions containing e.g. organic phosphorous containing compounds, and according to (ii), e.g. bicarbonate, halogenated hydrocarbon and carbon dioxide containing compositions.
For a generally applicable fire-extinguishing composition, it is desirable that the composition has additional fire retarding properties in accordance with the first (i) general principle above. The reason for this is to be found in the mechanisms by which a fire spreads and re-ignites. A fire spreads by ignition of the material adjacent to the burning material, either by direct contact with the flames or indirectly by the heat radiation. Hence, if the materials tendency to kindle is lowered by the fire-extinguishing composition, the spreading of the fire is inhibited and the extinguishing of the same facilitated. Furthermore, when the flames have been put out, the chances of subsequent re-ignition are diminished in comparison to the case of employment of fire- extinguishing means which are lacking additional fire retarding properties.
Additional desirable properties of a generally applicable fire-extinguishing composition, beside its effectiveness as flame retardant and fire extinguisher, include:
• Low toxicity.
• Low environmental impact.
• Low cost of composing constituents
• Easy preparation and handling, e.g. by firefighters.
· No smell or a pleasant smell. • High stability enabling long term storage without decomposition and/or physical changes, e.g. precipitation, of the composition.
• Suitable physicochemical properties, e.g. viscosity, density and lipophilicity, to allow facile and controlled application by e.g. the spraying through nozzles and/or pumping through fire-hoses.
• Suitable pseudoplasticity or thixotropy to maximize the adhesion of the composition to the material adj acent to the burning material.
The most well known and used fire-extinguishing composition, which fulfills many of the above mentioned desired properties, is common water. When used in fire- fighting, water contacts burning objects which results in sufficient cooling such that the burning objects fall below their combustion or ignition temperatures, and new ignition is precluded. In addition, when water contacts hot objects, the water vaporizes to produce steam, which expands and expels the air necessary for combustion.
However, when a fire is extinguished by spraying water on the fire, only a part of the sprayed water is effective because of water loss, such as by run-off or
evaporation.
In order to improve the properties of water in flame proofing and fire-fighting applications, additives such as fire retarding chemicals, which may retard combustion for at least brief periods even after the water has evaporated, as well as having a direct fire-extinguishing effect, are being developed and are presently in use. Additional additives include, for example, thickening agents and different foam forming agents. Various forms of organic and inorganic phosphorous containing compounds represent commonly used fire retarding chemicals.
EP1065309 Al describes a composition for fire protection treatment of textile materials consisting of an aqueous solution of carbamide and a complex of the ammonium salt of an amidoalkylphosphonic acid and ammonium chloride. The same or a similar composition can be obtained by dissolution of a commercially available product named Noflan®. In addition, a process for fireproofing treatment of textile materials by employment of this composition is also described. The textile material, which is first allowed to undergo an impregnation with a melamine-type resin and/or silicon-containing compounds in order to achieve e.g. a good fixation of the
phosphorous containing flame retarder, is subsequently treated with the composition, before heat treatment at elevated temperature. One disadvantage of this composition is the multistep procedure utilized for the fireproofing treatment and e.g. the equipment needed for heating the material which is being fireproofed. Furthermore, this composition is not well suited for storage over prolonged time periods due to physical and/or chemical change and decomposition, respectively.
EP1418178 Al discloses the ammonium salt of nitrilotris(methylene) triphosphonic acid amide, which is useful as a flame retardant of polymeric materials by addition to the polymer at the stage of polymer processing, and may be used for the fireproofing of e.g. textiles by treating the same with the corresponding aqueous formulation.
GB2299094 A discloses an aqueous formulation comprising a polymer in which an organic phosphorous containing compound has been bonded to the same. This formulation may be used for the fire proofing of e.g. textiles. The organic phosphorous containing compounds, acting as starting materials to be bonded to suitable reactive functional groups of the polymer, include dialkyl phosphites, oligomers of
vinylphosphonic esters, oxoacids of phosphorus and their corresponding salts, and esters or salts of methylphosphonic acid. The material treated with the aqueous formulation, e.g. a textile, is preferably subsequently treated at an elevated temperature in a drying oven in order to enhance the integrity of the polymer and/or complete the bonding of the organic phosphorous containing compound to the polymer.
A disadvantage, common to all of the above aqueous formulations and compositions (described in EP1065309 Al, EP1418178 Al and GB2299094 A), include the non-optimal physical chemical properties for the application of the same by e.g. spraying or sprinkling. Furthermore, all of the above documents (EP1065309 Al, EP1418178 Al and GB2299094 A) fail to mention use of the respective formulation or composition in fire-extinguishing applications.
Hence, an improved formulation useful for fire fighting, including fire extinguishing and fire proofing, would be advantageous. SUMMARY OF THE INVENTION
It is an object of the present invention, to provide a generally applicable fire- extinguishing composition for solid materials.
It is another object of the present invention, to provide a composition which is effective both as flame retardant and fire extinguisher.
It is another object of the present invention, to provide a composition which effectively prevents ignition of solid material adjacent to burning material.
It is another object of the present invention, to provide a composition which is effective as fire extinguisher and/or flame retardant and which simultaneously has a maximized adhesion to a surface onto which it has been applied.
It is another object of the present invention, to provide a composition which is effective as fire extinguisher and/or flame retardant and which simultaneously exhibits all of the following properties: low toxicity, environmentally friendly, easy preparation and handling, suitable for long term storage and suitable physicochemical properties to allow facile and controlled application.
These and other objects, which will appear from the following description, have now been achieved by a composition, such as e.g. an aqueous composition, according to the present invention, which comprises an organic phosphorous containing compound and a rheology modifier. The organic phosphorous containing compound is a compound of formula (I),
Figure imgf000005_0001
or a complex, solvate or hydrate thereof, wherein M is selected from the group consisting of H, H4, Na and K, and R is Ci-6 alkyl or a substituent according to formula (II) (CH2)n
(CH^n N (CH2)n
NH, NH;
(Π)
Q of the substituent according to formula (II) is independently selected from the group consisting of H, H4, Na and K, and n is an integer number from 1 to 3. The composition according to the present invention may be used in fire control applications such as, for example, fire extinguishing of burning solid materials and for flame retardation of solid materials.
Further features of the invention and its embodiments are set forth in the appended claims. DETAILED DESCRIPTION OF THE EMBODIMENTS
Several embodiments of the present invention will be described in more detail below with reference to the accompanying formulas in order for those skilled in the art to be able to carry out the invention. The invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. The embodiments do not limit the invention, but the invention is only limited by the appended patent claims. Furthermore, the terminology used in the detailed description of the particular embodiments illustrated in the accompanying drawings is not intended to be limiting of the invention.
The disclosed composition essentially comprises an organic phosphorous containing compound and a rheology modifier, such as xhantan gum, and optionally at least one additional additive, such as a preservative. The disclosed composition is preferably, but not necessarily, an aqueous composition, i.e. the main constituent, besides the organic phosphorous containing compound, the rheology modifier and the optional additive(s), is preferably but not necessarily water. Water is advantageous due to its low toxicity and its low cost etc. Other non-flammable main constituents are, however, potentially useful as solvents for the organic phosphorous containing compound, the rheology modifier and the optional additive(s) of the composition of the invention. Examples of such non-flammable main constituents include carbon dioxide, such as supercritical carbon dioxide, non-flammable halogenated hydrocarbons, such as polyfluorinated hydrocarbons, or any other non-flammable liquid, such as nonflammable liquids presently or previously used in fire-extinguishing applications, as well known by the skilled artisan.
The rheology modifier of the composition turns its viscosity to be dependent on shear rate and/or shear rate history. The non-Newtonian, e.g. tixotropic or pseudoplastic, properties of the composition, in combination with the organic phosphorous containing compound, are highly beneficial in fire-control applications. For example, when the disclosed composition is pumped through e.g. a nozzle towards a burning material, it attains a fluid like form and is easily and well spread. When it has reached the burning material, or objects adjacent to the burning material, it attains a stable gel like form and the tendency of the composition to run off the same or to be blown away by the wind is minimized. Hence, a highly effective flame retardation of the adjacent objects is achieved, whereby the fire is effectively hindered from spreading while it is
simultaneously being extinguished.
According to one embodiment, the organic phosphorous containing compound may be a compound of formula (I) and complexes, e.g. the ammonium chloride complex, or solvates or hydrates thereof, or a commercially available product which contains at least one compound represented by formula (I) as a main constituent.
Figure imgf000007_0001
(I)
The generic molecular fragments of a compound of formula (I) are represented by the following molecular fragments, in which:
M may be selected from the group consisting of H, NH4, Na and K; and
R may be Ci-6 alkyl, e.g. methyl, ethyl, ^-propyl and /'-propyl, or a substituent according to formula (II).
The generic molecular fragments of the substituent of formula (II) are represented by the following molecular fragments, in which: Q may be independently selected from the group consisting of H, H4, Na and
K; and
"n" may be an integer number from 1 to 3, denoting the number of methylene- groups connected to each other to form a linkage between the nitrogen atom and the phosphorous atom.
\
\
-(CH^
Figure imgf000008_0001
(CH2)rr
NH, NH;
(Π)
It was surprisingly found that the composition according to the invention constitute an excellent fire fighting composition for solid materials, with fire extinguishing and fire retarding properties.
With "fire-extinguish" or simply "extinguish" with reference to flames or fire, or the like, is to be understood herein a treatment which puts out the flames of a fire. With "flame proofing", "fire proofing", "flame retardation", "fire retardation", or the like, is to be understood herein a treatment which lowers a materials tendency to kindle, such as, for example, impregnation.
Much of the unexpected effectiveness and many the unforeseen advantages of the composition according to the invention are due to the simultaneous presence therein of the organic phosphorous containing compound and the rheology modifier.
Without being bound to any theory, the inventor believes that the relatively low viscosity of the composition at the time it is pumped through e.g. a nozzle or the like, is causing the formation of small drops which are well spread towards the burning material and/or adjacent material which is not yet burning but face a risk of being ignited. When these drops adhere to the burning material or the adjacent material, they form a film with a relatively high viscosity. Due to the relatively high viscosity, the film is well adhered to the material without running off and thereby effective as a flame retardant for material adjacent to burning material. The combination of the disclosed compositions fire extinguishing properties and the above described function as an effective flame retardant is advantageous in comparison to Newtonian fire extinguishing compositions of the prior art.
The composition may be used for the extinguishing of fires in combustible solid materials for which conventional fire fighting means are presently employed including, for example, wood (e.g. forest fires), paper, textile, plastic materials, rubber, such as in car tires, and industrial waste. The composition may also be used for flame proofing of such combustible solid materials or other objects. For example, the composition may be sprayed towards objects, e.g. trees, houses, ships, airplanes or the like, which are adjacent to or near a fire to prevent the fire from spreading to these objects.
One advantage of the composition in comparison to other flame retarding agents of the prior art with regard to fire fighting of burning solid materials, for example wood and tree-based materials, is its excellent flame retarding properties upon direct administration by e.g. spraying. The suitable physicochemical properties of the composition, for example its relatively low viscosity when sprayed but relatively high viscosity when adhered, enables an even spread of the composition on the surface of the solid material without running of the same. The close and long contact with the solid material then enables the phosphorous containing compound of the disclosed
composition to effectively penetrate and flame proof the material.
Examples of solid materials, of which the flames when burning may be extinguished with the composition of the invention, include wood, trees, sawdust, paper, textile, house-refuse and industrial waste.
According to one embodiment, the herein mentioned solid materials may be flame proofed by treatment with the composition according to the invention.
The constituents of the composition according to the invention may be either commercially available products, available at a low cost, or easily prepared from cheap commercially available chemicals.
The composition according to the invention may be a solution or colloid with a homogenous appearance. It may be stable in respect of no, or minimal, observation of either of discoloration, precipitation, flocculation, creaming, breaking or coalescence when stored over relevant time-periods, e.g. over several months or a year at room temperature or 20 to 30°C. Thus, it is well suited for storage in e.g. tanks or containers, such as fire-extinguishers, in order to be readily available in case of a fire which needs to be extinguished. Preferably, such containers are made of a material that is not reacting chemically with the composition, for example, a suitable plastic material or stainless steel.
The relative proportions of the constituting ingredients, e.g the organic phosphorous containing compound and the rheology modifier, of the disclosed composition, may be varied so that a composition which is optimal for the particular fire fighting or fire retarding application is obtained, as well known to the skilled person. For example, the physical properties, e.g. the viscosity, may be fine-tuned by varying the relative proportions of the constituting ingredients to generate the desired drop-size and/or stream-shape as the composition is discharged through a particular nozzle, or other type of outlet, used in the application of the same.
Furthermore, the selection of the constituting ingredients within the scope of the invention may be chosen such that a composition which is optimal for the particular fire fighting or fire retarding application is obtained, as well known to the skilled person. For example, the combination of a particular organic phosphorous containing compound, rheology modifier and preservative may be chosen to optimize the stability of the composition so that no or minimal precipitation, or any other physical change, occurs upon storage of the composition in e.g. reservoirs at sites where readily available fire fighting capabilities are desired.
Another example, according to one embodiment, include the addition of a suitable dyestuff to the composition for the fire-fighting of e.g. forest fires, whereby treated areas are easily spotted, as known in the art.
In one non-limiting fire-fighting application according to one embodiment, the composition may be used to pre-treat, by e.g. spraying, materials or objects in order to flame proof these. Such materials and objects include, for example, houses located near a raging fire and trees located near a raging forest-fire. The physicochemical properties of the composition, which is making the composition facile to spread in an effective way, is advantageous in this application.
According to one embodiment of the invention, the rheology modifier of the composition may be selected from the group consisting of tixotropy enhancing or pseudoplasticity enhancing polysaccharides known in the art. The rheology modifier may also be any other organic or inorganic compound as known in the art with a tixotropy enhancing or pseudoplasticity enhancing effect similar to the tixotropy enhancing or pseudoplasticity enhancing effect of a suitable polysaccharide, such as xanthan gum. According to one embodiment of the invention, the rheology modifier of the composition may be xanthan gum. Advantages of xanthan gum include its readily availability, low cost and low toxicity.
According to one embodiment of the invention, the composition may comprise at least one preservative with e.g. antibacterial and antifungal effects to increase the long term storage capabilities of the composition at e.g. 20 to 30 °C to at least e.g. one year. Examples of suitable preservatives include N-alkylisothiazolinones such as e.g. 2- methyl-2H-isothiazol-3-one, chlorinated N-alkylisothiazolinones such as e.g. 5-chloro- 2-methyl-2H-isothiazol-3-one, ethylparaben, benzalkonium chloride, 2-bromo-2- nitropropane-l,3-diol, or the like.
According to one embodiment of the invention, the composition may comprise 2-methyl-2H-isothiazol-3-one or 5-chloro-2-methyl-2H-isothiazol-3-one as
preservative.
According to one embodiment of the invention, the composition may comprise a mixture of 2-methyl-2H-isothiazol-3-one and 5-chloro-2-methyl-2H-isothiazol-3-one, such as in commercially available Kathon CG® or as a mixture in the range from 1 :99 to 99: 1 by weight, respectively, as preservative.
According to one embodiment of the invention, the organic phosphorous containing compound may be commercially available Noflan®, the rheology modifier may be commercially available xanthan gum, and the composition may additionally comprise 2-methyl-2H-isothiazol-3-one or 5-chloro-2-methyl-2H-isothiazol-3-one, or any mixture thereof, as preservative.
According to one embodiment of the invention, the organic phosphorous containing compound may be a compound of formula (I), or the ammonium chloride complex thereof, wherein R is methyl, ethyl, ^-propyl or /'-propyl, and M is H4; the rheology modifier may be commercially available xanthan gum; and the preservative may be 2-methyl-2H-isothiazol-3-one or 5-chloro-2-methyl-2H-isothiazol-3-one, or any mixture thereof.
According to one embodiment of the invention, there is provided a
composition comprising 1 to 30 % by weight of the organic phosphorous containing compound and 0.01 to 3 % by weight of the rheology modifier.
According to a preferred embodiment of the invention, there is provided a composition comprising 5 to 25 % by weight of the organic phosphorous containing compound and 0.01 to 1 % by weight of the rheology modifier. According to one embodiment of the invention, there is provided a composition comprising 0.01 to 0.5 %, such as 0.04 to 0.1 %, by weight of a preservative selected from the group consisting of 2-methyl-2H-isothiazol-3-one, 5-chloro-2-methyl-2H- isothiazol-3-one, and a mixture of 2-methyl-2H-isothiazol-3-one and 5-chloro-2- methyl-2H-isothiazol-3-one.
According to one embodiment of the invention, the organic phosphorous containing compound may be commercially available Noflan®.
According to one embodiment of the invention, the organic phosphorous containing compound may be the compound of formula (I).
According to one embodiment of the invention, the organic phosphorous containing compound may be the compound of formula (I), or the ammonium chloride complex thereof, wherein R is methyl, ethyl, ^-propyl or /'-propyl, and M is H4.
According to one embodiment of the invention, the organic phosphorous compound may be a compound of formula (I), wherein R is a substituent according to formula (II), M is H4, Q is H4, and n is 1.
According to one embodiment of the invention, the composition may be practically pH-neutral, i.e. its pH may be > 4, preferably > 6, and < 10, preferably < 8. The pH of the composition may be adjusted accordingly with a suitable base, such as NaOH, or a suitable acid, such as HC1, or any other suitable base or acid as known in the art.
According to one embodiment of the invention, an additive of the composition of the present invention is a nitrogen containing compound. Several nitrogen containing compounds are known in the art to act as fire retardants. Hence, such an additive has the advantage of further enhance the fire retarding properties of the composition according to the invention.
According to one embodiment of the invention, the organic phosphorous containing compound is the compound of formula (I), and an additive is a nitrogen containing compound. The proportion of the nitrogen containing compound is in the range of 5 to 25 % by weight relative the compound of formula (I), preferably 8 to 12 %.
According to one embodiment of the invention, an additive of the composition of the present invention is urea.
According to one embodiment of the invention, the nitrogen containing additive of the composition is a fire retarding compound as known in the art, for example, a 1,3,5-triazine derivative, e.g. melamine; a heptazine derivative, e.g. melem and melon; and a cyanuric acid derivative, e.g tris-2-hydroxy ethyl isocyanurate.
According to one embodiment of the invention, additional additives of the composition of the present invention comprise, for example, suitable magnesium-, aluminum-, zink-, and calcium salts, known in the art to have a fire retarding effect, including, for example, magnesium hydroxide, aluminum hydroxide, zinc
hydroxystannate, calcium cyanamide, zinc cyanamide, boric acid, zinc borate and other boric acid salts. One or several of these additives may further enhance the fire protecting properties of the composition according to the invention.
According to one embodiment of the invention, additional additives of the composition of the present invention comprise, for example, heat or light stabilizers, lubricants, film-forming agents, plasticizers, colorants, pigments, dyestuffs,
hydrophilizing agents, hydrophobizing agents and thickeners. Such additives may further enhance the stability, the fire fighting capability, the ease of spotting where the composition has been applied, and improve the physicochemical properties of the composition to be more optimal for the particular application. The selection of a particular one of these additives for the enhancement or improvement of a given property, is known to the one skilled in the art.
According to one embodiment of the invention, an additional additive of the composition of the present invention may be a foam forming agent, as well known in the art, which results in the generation of, for example, an aqueous film forming foam, an alcohol-resistant aqueous film forming foam, and a film formed from fluoroproteins.
According to one embodiment of the invention, an additional additive of the composition of the present invention may be an anti-freeze agent such as ethylene- or propylene glycol. The composition may then be stored at temperatures below freezing point, for example outdoors, without solidification.
According to one embodiment of the invention, the composition of the invention may be used as the main active fire fighting component in an active fire protection device. Such an active fire protection device may be a hand held or cart- mounted fire extinguisher used to extinguish or control small fires. A suitable propellant, for example nitrogen, air, or carbon dioxide, may be used.
According to one embodiment, the composition may be used for fire extinguishing or fire retardation of fires of fire class A, according to the European or American classification system. According to one embodiment, the composition may be used for fire control of a solid including, for example, wood, trees, sawdust, paper, textile, house-refuse, rubber, such as in car tires, and industrial waste.
According to one embodiment of the invention, the composition may comprise 5 to 25 % by weight of commercially available Noflan®, 0.01 to 1 % by weight of commercially available xanthan gum, and 0.04 to 0.1 %, by weight of a commercially available mixture of 2-methyl-2H-isothiazol-3-one and 5-chloro-2-methyl-2H- isothiazol-3-onem, such as an 1 :3 mixture.
One embodiment of the invention is illustrated by the following example describing the preparation of an exemplary composition according to the invention:
To a borosilicate glass container was added commercially available Noflan® (1500 g). Hot water (10.0 liter), with a temperature being kept within the range of 50 to 65 °C, was thereafter added under vigorous mechanical stirring. The mixture was thereafter vigorously mechanically stirred for 4 hours while being allowed to reach room temperature (25 °C). A mixture of 5-chloro-2-methyl-2H-isothiazol-3-one and 2- methyl-2H-isothiazol-3-one (8.0 g, 3 : 1 by weight), followed by xantan gum (60 g) , was thereafter added under vigorous mechanical stirring. The mixture was thereafter vigorously mechanically stirred for 4 hours to yield a composition according to the invention.
In the claims, the term "comprises/comprising" does not exclude the presence of other elements or steps. Furthermore, although individually listed, a plurality of means, elements or method steps may be implemented by e.g. a single unit or processor. Additionally, although individual features may be included in different claims, these may possibly advantageously be combined, and the inclusion in different claims does not imply that a combination of features is not feasible and/or advantageous. In addition, singular references do not exclude a plurality. The terms "a", "an", "first", "second" etc do not preclude a plurality. Reference signs in the claims are provided merely as a clarifying example and shall not be construed as limiting the scope of the claims in any way.

Claims

1. A composition comprising an organic phosphorous containing compound and a rheology modifier, said organic phosphorous containing compound being a compound of formula (I),
R P NH2
O M
O ,
or a complex, solvate or hydrate thereof, wherein:
M is selected from the group consisting of H, NH , Na and K;
R is Ci-6 alkyl or a substituent according to formula (II),
O P (CH^
NH,
Figure imgf000015_0001
independently selected from the group consisting of H, NH4, Na and K; and
integer number from 1 to 3
2. A composition according to claim 1, wherein M is NH4 and R is C1 -3 alkyl.
3. A composition according to any one of the preceding claims, wherein said organic phosphorous containing compound is a complex with ammonium chloride.
4. A composition according to any one of the preceding claims, wherein said rheology modifier is a polysaccharide.
5. A composition according to claim 4, wherein said polysaccharide is xanthan gum.
6. A composition according to any of the preceding claims, wherein said composition comprises 1 to 30% by weight of said organic phosphorous containing compound and 0.01 to 3% by weight of said rheology modifier.
7. A composition according to any of the preceding claims, further comprising a preservative.
8. A composition according to claim 7, wherein said preservative is selected from the group consisting of an N-alkylisothiazolinone, a chlorinated N- alkylisothiazolinone , ethylparaben, benzalkonium chloride and 2-bromo-2- nitropropane-l,3-diol.
9. A composition according to claim 7 or 8, wherein said composition comprises 0.01 to 0.5% by weight of said preservative.
10. A composition according to any of the preceding claims, wherein said composition is an aqueous composition.
11. A composition according to any one of the preceding claims, further comprising at least one additive selected from the group consisting of a nitrogen containing compound, a fire retarding magnesium-, aluminum-, zink-, or calcium salt, a heat or light stabilizer, a lubricant, a film-forming agent, a foam forming agent, an antifreeze agent, a plasticizer, a dyestuff, a hydrophilizing agent, a hydrophobizing agent, and a thickener.
12. Use of a composition according to any of the preceding claims in fire control application.
13. Use according to claim 12, wherein said fire control application is fire extinguishing or flame proofing.
14. Use according to any one of claims 12 or 13, wherein said fire control application is fire control of a solid material.
15. Use according to any one of claims 12 to 14, wherein said composition is an active component in an active fire protection device, said device being a hand held cart-mounted fire extinguisher.
PCT/SE2012/050101 2011-02-03 2012-02-02 Composition and method for fire control WO2012105903A1 (en)

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US9919174B2 (en) 2012-09-30 2018-03-20 Flame Security Sweden Ab Aqueous composition comprising phosphorous and nitrogen for general fire control

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EP1418178A1 (en) * 2001-07-16 2004-05-12 Isle Firestop Ltd. Flame retardant for polymeric materials

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Publication number Priority date Publication date Assignee Title
GB2021407A (en) * 1978-05-26 1979-12-05 Monsanto Co Chemical retardants for forest fires
WO2002043813A1 (en) * 2000-11-28 2002-06-06 Astaris Llc Biopolymer thickened fire retardant compositions
EP1418178A1 (en) * 2001-07-16 2004-05-12 Isle Firestop Ltd. Flame retardant for polymeric materials

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9919174B2 (en) 2012-09-30 2018-03-20 Flame Security Sweden Ab Aqueous composition comprising phosphorous and nitrogen for general fire control
CN104941105A (en) * 2014-03-31 2015-09-30 文联煜 Triazine nitrogen heterocyclic ring polymer extinguishing agent applicable to warships and aircraft carriers

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