US20070194289A1 - Fire resistant material - Google Patents

Fire resistant material Download PDF

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US20070194289A1
US20070194289A1 US10/533,579 US53357903A US2007194289A1 US 20070194289 A1 US20070194289 A1 US 20070194289A1 US 53357903 A US53357903 A US 53357903A US 2007194289 A1 US2007194289 A1 US 2007194289A1
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ioh
melamine
formulation
fire resistant
cyanurate
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Matthew Anglin
Stuart Bateman
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Boeing Co
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Commonwealth Scientific and Industrial Research Organization CSIRO
Boeing Co
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Assigned to BOEING COMPANY, THE reassignment BOEING COMPANY, THE ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: COMMONWEALTH SCIENTIFIC AND INDUSTRIAL RESEARCH ORGANISATION
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
    • C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
    • C01B33/44—Products obtained from layered base-exchange silicates by ion-exchange with organic compounds such as ammonium, phosphonium or sulfonium compounds or by intercalation of organic compounds, e.g. organoclay material
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K2003/343—Peroxyhydrates, peroxyacids or salts thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S57/00—Textiles: spinning, twisting, and twining
    • Y10S57/904—Flame retardant

Definitions

  • the present invention relates to inorganic-organic hybrids (IOHs), methods for their preparation and their use as fire resistant materials or components of fire resistant materials. More specifically, the invention relates to polyamide fire resistant formulations containing IOHs which have application in the production of fire resistant articles or parts thereof for use in the transportation, building, construction and electrical or optical industries.
  • IOHs inorganic-organic hybrids
  • polyamide fire resistant formulations containing IOHs which have application in the production of fire resistant articles or parts thereof for use in the transportation, building, construction and electrical or optical industries.
  • flame-retarding species may be added during processing or forming of the materials to reduce the end products flammability.
  • Conventional flame-retardants may be divided into different categories including:
  • Halogen based which consist of either brominated or chlorinated chemicals such as brominated polystyrene or phenylene oxide (Dead Sea Bromine or Great Lakes CC) or bis(hexachlorocyclopentadieno) cyclooctane (Occidental CC).
  • Phosphorus based which consist of a range of different chemistries from elemental phosphorus (Clarient), phosphonates (A&W antiblaze 1045), phosphonate esters (Akzo Nobel), phosphites, phosphates and polyphosphates including melamine phosphite and phosphate, ammonium and melamine polyphosphate (DSM Melapur).
  • Nitrogen based; such as melamine and its salts U.S. Pat. No. 4,511,684 Schmidt & Hoppe.
  • Intumescent agents incorporating (i) an acid source (carbonization catalyst) such as ammonium polyphosphate; (ii) a carbonization reagent e.g. polyhydric alcohols such as pentaerythritol; and (iii) a blowing reagent like melamine.
  • an acid source such as ammonium polyphosphate
  • a carbonization reagent e.g. polyhydric alcohols such as pentaerythritol
  • a blowing reagent like melamine Expandable graphite is also known to undergo thermal expansion on addition of heat.
  • Inorganic additives such as magnesium hydroxide and aluminum hydroxide (Martinswerk), zinc borate (Fire Brake ZB, US Borax) and antimony trioxide.
  • organically modified clay may be nano-dispersed into polymeric materials to improve mechanical and fire performance.
  • Morton (WO 99/43747, (1999) General Electric Company) teaches that in certain polyester blends, phosphorus based flame retardants especially resorcinol diphosphate and organically modified clay act synergistically to improve fire performance. No mention, however, is made of other important aspect such as the effect on mechanical performance, smoke and toxic gas emission.
  • an inorganic-organic hybrid which comprises:
  • the organic component of the IOH also includes one or more neutral organic components which are intercalated between and/or associated with the layer(s) of the inorganic component.
  • a method for the preparation of the IOH defined above which comprises mixing components (i) and (ii) defined above or constituents thereof in one or more steps.
  • the present invention also provides the use of the IOH defined above as a fire resistant material.
  • a fire resistant formulation which comprises:
  • a method for the preparation of the fire resistant formulation defined above which comprises mixing components (i) and (ii) as defined above or constituents thereof in one or more steps.
  • the present invention also provides a polyamide fire resistant formulation which comprises either:
  • the present invention further provides a method for the preparation of the polyamide fire resistant formulation defined above which comprises dispersing the IOH or the fire resistant formulation defined above or constituents thereof into the polyamide based matrix in one or more steps.
  • the IOH and/or fire resistant formulations of the present invention may be used to produce fire resistant articles or parts thereof.
  • the present invention provides a fire resistant article or parts thereof which is composed wholly or partly of the IOH and/or fire resistant formulations defined above.
  • the present invention also provides a method of preparing the fire resistant article or parts thereof defined above which comprises moulding or forming the IOH and/or fire resistant formulations defined above.
  • the inorganic component is a swellable/expandable layered inorganic based material, rendered positively (or negatively) charged due to isomorphic substitution of elements within the layers, such as, those based on a 1:1 layered silicate structure such as kaolin and serpentine and a 2:1 layered silicate structure such as phyllosilicates, talc and pyrophyllite.
  • layered minerals include layered double hydroxides of the general formula Mg 6 Al 3.4 (OH) 18.8 (CO 3 ) 1.7 .H 2 O including hydrotalcites and synthetically prepared layered materials including synthetic hectorite, montmorillonite, fluorinated synthetic mica and synthetic hydrotalcite.
  • the group consisting of naturally occurring or synthetic analogues of phyllosilicates is particularly preferred.
  • This group includes smectite clays such as montmorillonite, nontronite, beidellite, volkonskoite, hectorite, bentonite, saponite, sauconite, magadiite, kenyaite, laponite, vermiculite, synthetic micromica (Somasif) and synthetic hectorite (Lucentite).
  • Other useful layered minerals include illite minerals such as ledikite and mixtures of illite minerals with said clay minerals.
  • Naturally occurring phyllosilicates such as bentonite, montmorillonite, and hectorite are most preferred.
  • Such phyllosilicates with platelet thicknesses less than about 5 nanometers and aspect ratios greater than about 10:1, more preferably greater than about 50:1 and most preferably greater than about 100:1 are particularly useful.
  • the preferred inorganic materials generally include interlayer or exchangable metal cations to balance the charge, such as, alkali metals or alkali earth metals, for example, Na + , K + , Mg 2+ or Ca 2+ , preferably Na + .
  • the cation exchange capacity of the inorganic material should preferably be less than about 400 milli-equivalents per 100 grams, most preferably about 50 to about 200 milli-equivalents per 100 grams.
  • the organic component includes one or more ionic species that may be exchanged with the exchangeable metal ions associated with the inorganic component and optionally one or more neutral organic species which are intercalated between and/or associated with the layer(s) of the inorganic component and/or one or more coupling reagents.
  • association with is used herein in its broadest sense and refers to the neutral organic component being attached to the layer(s) of the inorganic component, for example, by secondary bonding interactions, such as, Van der Waals interactions or hydrogen bonding or trapped by steric limitation.
  • ionic species include those that contain onium ions such as ammonium (primary, secondary, tertiary and quaternary), phosphonium or sulfonium derivatives of aliphatic, aromatic or aryl-aliphatic amines, phosphines and sulfides.
  • onium ions such as ammonium (primary, secondary, tertiary and quaternary), phosphonium or sulfonium derivatives of aliphatic, aromatic or aryl-aliphatic amines, phosphines and sulfides.
  • Such compounds may be prepared by any method known to those skilled in the art. For example, salts prepared by acid-base type reactions with mineral or organic acids including hydrochloric, sulfuric, nitric, phosphoric, acetic and formic acids, by Lewis-acid-Lewis-base type reactions or by reaction with alkyl halides to form quaternary salts for example using Kohlutkin type methodology.
  • Ionic or neutral compounds which are known to decompose or sublime endothermically, and/or which release volatiles with low combustibility on decomposition and/or induce charring of organic species during thermal decomposition or combustion are particularly preferred.
  • Suitable species include neutral or ionic derivatives of nitrogen based molecules, such as, triazine based species, for example, melamine, triphenyl melamine, melam (1,3,5-triazine-2,4,6-triamine-n-(4,6-diamino-1,3,5-triazine-yl)), melem ((-2,5,8-triamino-1,3,4,6,7,9,9b-heptaazaphenalene)), melon (poly ⁇ 8-amino-1,3,4,6,7,9,9b-heptaazaphenalene-2,5-diyl)imino ⁇ ), bis and triaziridinyltriazine, trimethylsilyltriazine, melamine cyanurate, melamine phthalate, melamine phosphate, melamine phosphite, melamine phthalimide, dimelamine phosphate, phosphazines and/or low molecular weight polymers
  • Reagents known to induce charring of organic species include derivatives of phosphoric acid or boric acid, such as ammonia polyphosphate and melamine polyphosphate, melamine phosphate ammonium borate.
  • the preferred ionic compounds may be optionally used in combination with other ionic compounds, for example, those known to improve compatibility and dispersion between the layered inorganic material and polymeric matrices such as those described in WO 93/04118 for the preparation of nanomaterials.
  • Amphiphilic molecules that incorporate a hydrophilic ionic group along with hydrophobic alkyl or aromatic moieties are preferred.
  • One or more coupling reagents may also be associated with the inorganic component.
  • Suitable coupling reagents include organically functionalised silanes, zirconates and titanates.
  • silane coupling reagents include tri-alkoxy, acetoxy and halosilanes functionalised with amino, epoxy, isocyanate, hydroxyl, thiol, mercapto and/or methacryl reactive moieties or modified to incorporate functional groups based on triazine derivatives, long chain alkyl, aromatic or alkylaromatic moieties.
  • zirconate and titanate coupling reagents include Teaz and Titan1.
  • metal cations or anions associated with layered inorganic materials may be exchanged with organic ions through ion exchange processes.
  • the layered inorganic material is first swollen or expanded in a suitable solvent(s) prior to ion exchange and then collected from the swelling solvent following agglomeration using methods such as filtration, centrifugation, evaporation or sublimation of the solvent.
  • Ion exchange techniques with suitable molecules are known to be a useful method of increasing the compatibility between clay and organic polymeric binders, thus aiding dispersion of clay platelets into polymeric based matrices on a nanometer scale.
  • the ion exchange process may be optionally carried out in the presence of one or more types of organic ion to produce an inorganic-organic hybrid with a plurality of functions.
  • functions may include the presence of ions which promote dispersion, compatibility and interactions with the plastic matrix and ions useful to improve other properties such as fire performance.
  • the organic ions are added in molar excess of the ion exchange capacity of the inorganic material, preferably less than about 10-fold excess, more preferably less than about a 5-fold excess is required.
  • the ion exchange processes may be carried out in the presence of functional dissolved or partially dissolved neutral species. Without being limited by theory, it is proposed that at least a portion of the neutral species are trapped in the intergallery region or otherwise associated with the layered inorganic material following ion exchange. Such a process provides a useful mechanism of dispersing neutral additives on a molecular level into plastics. Again without being limited by theory, during melt processing at least partial exfoliation of the inorganic-organic hybrid allows the neutral molecules to diffuse away and become homogeneously dispersed with the matrix on a molecular level. This has a major impact on the performance of the resultant material since it is well known that efficient dispersion of all components in a plastic formulation, preferably on a nano- or molecular scale, is an important factor for achieving optimum performance.
  • the IOH may be treated prior, during or following ion exchange with one or more coupling reagents as described above.
  • the coupling reagents are derivatized to improve, for example, the compatibility and interactions between the inorganic phase and polymeric matrix or to attach other desirable functionalities to the inorganic layered phase.
  • Suitable flame retardants which retard flame propagation, heat release and/or smoke generation which may be added singularly or optionally synergistically to the IOH include:
  • Phosphorus derivatives such as molecules containing phosphate, polyphosphate, phosphites, phosphazine and phosphine functional groups, for example, melamine phosphate, dimelamine phosphate, melamine polyphosphate, ammonia phosphate, ammonia polyphosphate, pentaerythritol phosphate, melamine phosphite and triphenyl phosphine.
  • Nitrogen containing derivatives such as melamine, melamine cyanurate, melamine phthalate, melamine phthalimide, melam, melem, melon, melam cyanurate, melem cyanurate, melon cyanurate, hexamethylene tetraamine, imidazole, adenine, guanine, cytosine and thymine.
  • Molecules containing borate functional groups such as ammonia borate and zinc borate.
  • Molecules containing two or more alcohol groups such as pentaerythritol, polyethylene alcohol, polyglycols and carbohydrates, for example, glucose, sucrose and starch.
  • Molecules which endothermically release non-combustible decomposition gases such as, metal hydroxides, for example, magnesium hydroxide and aluminum hydroxide.
  • the polyamide based matrix may be included in the fire resistant formulation in pellet, granule, flake or powdered form.
  • Suitable polyamides comprise generic groups with repeat units based on amides, such as, Nylon4, Nylon6, Nylon7, Nylon 11 and Nylon12, Nylon46, Nylon66, Nylon 68, Nylon610, Nylon612 and aromatic polyamides, for example, poly‘m’phenyleneisophthalamine and poly‘p’phenylene′terephthalmamide.
  • the polyamide based matrix may include co-polymers, blends and alloys.
  • the co-polymers may be made up of two or more different repeat units one of which is an amide.
  • Such co-polymers may be prepared by any suitable methods known in the art, for example, at the point of initial polymerisation or later through grafting or chain extension type reactions during processing.
  • the polyamide blends and alloys may be prepared using any method known to those skilled in the art including melt or solution blending. Blending or alloying the polyamide with other polymers may be desirable to improve properties such as toughness, modulus, strength, creep, durability, thermal resistance, conductivity or fire performance.
  • Nylon12, Nylon6 and Nylon66 and their respective co-polymers, alloys and blends are particularly preferred.
  • the polyamide formulation can also optionally contain one or more additives known in the art of polymer processing, such as, polymeric stabilisers, for example, UV, light and thermal stabilisers; lubricants; antioxidants; pigments, dyes or other additives to alter the materials optical properties or colour; conductive fillers or fibers; release agents; slip agents; plasticisers; antibacterial or fungal agents, and processing agents, for example, dispersing reagents, foaming or blowing agents, surfactants, waxes, coupling reagents, rheology modifiers, film forming reagents and free radical generating reagents.
  • additives known in the art of polymer processing such as, polymeric stabilisers, for example, UV, light and thermal stabilisers; lubricants; antioxidants; pigments, dyes or other additives to alter the materials optical properties or colour; conductive fillers or fibers; release agents; slip agents; plasticisers; antibacterial or fungal agents, and processing agents, for example, dispersing reagents
  • a particularly preferred formulation comprises
  • the polyamide formulation preferably contains a polyamide based matrix in an amount of from about 50 to about 95% w/w, an IOH in an amount less than about 25% w/w and optionally a flame retardant and/or additives in an amount less than about 30% w/w, but in some cases preferably above about 10% w/w.
  • the IOH may be readily dispersed into the polyamide based matrix during the compounding (mixing) stage. Without wishing to be limited by theory, it is proposed that ion exchange enhances the layered IOHs compatibility with polyamides compared with unmodified inorganic layered materials.
  • Dispersion of the various components of the fire resistant formulation including the IOH is aided by grinding prior to mixing. Grinding is achieved using any suitable grinding equipment including ball mills, ring mills and the like. It is preferable that the components including the IOH is ground to a particle size less than about 200 microns, more preferably less than about 50 microns, most preferably less than about 20 microns.
  • the hybrid material may also be ground using specialty grinding equipment allowing grinding to nanometer sizes.
  • Dispersion may be affected using any suitable melt, solution or powder based mixing process allowing sufficient shear rate, shear stress and residence time to disperse the IOH at least partially on a nanometer scale.
  • Such processes may be conducted using milling procedures such as ball milling, in a batch mixer using internal mixers, such as, Banbury and Brabender/Haake type mixers, kneaders, such as, BUS kneaders, continuous mixing processes including continuous compounders, high intensity single and twin screw extrusion.
  • twin screw extruders with an L:D ratio of at least about 24, preferably more than about 30 equipped with at least one and preferably multiple mixing and venting zones are employed for dispersion.
  • Such screw configurations useful for dispersive and distributive mixing are well known to those in the art.
  • a particularly useful system has been found to be that illustrated in FIG. 1 .
  • the components of the formulation may be added in any order or at any point along the extruder barrel. Since polyamides are susceptible to hydrolysis it is preferable that the components are dried prior to processing and/or mechanisms to remove water vapor such as vents or vacuum ports available during processing. In a preferred embodiment, all of the components are added at one end of the extruder. In another preferred embodiment, a polymeric binder and optionally minor components are added at one end of the extruder and the IOH and optionally minor components at a later point/s. In still another preferred embodiment, the IOH portion of the polymeric binder and optionally minor components are added at one end of the extruder with the remaining portion of the polymeric binder and optionally minor components are added at a later point/s. Following extrusion the molten composition is cooled by means of water bath, air knife or atmospheric cooling and optionally cut into pellets.
  • all of the major and minor components of the system can be combined in as few a mixing steps as possible, most preferably in a single mixing step.
  • the moulding or forming of the polyamide formulation into fire resistant articles or parts thereof can be carried out using any method known to those in the art including processes such as extrusion, injection moulding, compression moulding, rotational moulding, blow moulding, sintering, thermoforming, calending or combinations thereof.
  • the fire resistant polyamide system containing the major and minor components is moulded or formed into parts having wall thickness less than about 25 mm, preferably less than about 5 mm, most preferably less than 1.5 mm.
  • Such parts include but are not limited to tubes, complex moulded hollow parts, sheets and complex moulded sheets and other complex objects that are moulded or formed using techniques, such as, extrusion, injection moulding thermoforming and rotational moulding.
  • the article or part is directly produced during compounding for example by locating a die at the end of the extruder allowing the shape of the extrudate to be modified as required.
  • Such components include simple parts such as film, tape, sheet, tube, rod or string shapes.
  • the process may also involve multiple layers of different materials one of which being the said polymeric system built up by processes known to those in the art including co-extrusion.
  • the formulation is moulded or formed in a separate step using techniques such as injection, compression or blow moulding.
  • Such parts are generally more complex in nature compared with parts formed by extrusion alone, their design only limited by the requirements of the moulding tool/process employed. Suitable examples include but are not limited to stowage bin hinge covers, ECS duct spuds, latches, brackets, passenger surface units and the like.
  • the fire resistant polyamide formulation is ground to a powder.
  • grinding of the said formulation using cryogenic or atmospheric grinding techniques known to those in the art may be carried out without significantly effecting the performance of the system.
  • Such moulding applications include selective laser sintering, rotational moulding, and extrusion.
  • Suitable examples including but not limited to environmental control systems (air-conditioning ducts) and the like.
  • the polymeric formulation may be first formed into a sheet or film, for example, through extrusion, blow moulding, compression moulding or calending.
  • the sheet may be subsequently moulded to a desired shape using thermoforming techniques.
  • the sheet or film may be used to prepare reinforced thermoplastic laminates with woven fabrics prepared from surface modified or natural glass, carbon or aramid using techniques such as compression moulding or resin infusion/transfer.
  • the laminate sheet hence formed may be further moulded to a desired shape using techniques such as thermoforming.
  • the formulation may be spun into fibres by any method known to those skilled in the art. Such a process provides a method for producing fire resistant fabrics, carpets and alike
  • the present invention is useful for producing polyamide materials with favourable rheological properties for moulding including thin or intricate articles or parts thereof which maintain mechanical properties close to or exceeding that of the virgin polyamide matrix and which show improved fire performance in standard tests through resisting combustion by self-extinguishing when ignited, limiting flame propagation, and generating low smoke and toxic gas emissions.
  • Such articles or parts thereof are useful for applications which require superior fire performance and in industries that are regulated for fire performance including transport, for example, air, automotive, aerospace and nautical; building and construction; and electrical or optical, for example, cables, wires and fibres.
  • FIG. 1 is a diagram showing the twin screw extruder screw and barrel configuration
  • FIG. 2 is a graph showing the XRD results and transmission electron microscope (TEM) image for Example 7;
  • FIG. 3 is a graph showing the XRD results for Example 8.
  • FIG. 4 is a graph showing the XRD results for Example 9.
  • FIG. 5 is a graph showing XRD results for Example 17.
  • FIG. 6 is a picture of complex hollow fire resistant components moulded with formulations 13 and 34.
  • ASTM test samples Injection pressure gradient 800 to 600 bar, cavity pressure 400 bar, Holding pressures 600 to 0 bar Cooling time 30 sec Cone Calorimetry Samples: Injection pressure gradient 950 to 650 bar, cavity pressure 325 bar, Holding pressures 650 to 0 bar Cooling tine 60 sec Compression Assett 2.5 MPa pneumatic press, 45 cm platens, heating (400° C.) and cooling Moulding Moulding platen temperature 220° C. nylon12 Moulding platen temperature 260° C. nylon6 Moulding platen temperature 290° C. nylon66
  • results indicate that montmorillonite modified by melamine hydrochloride in the presence of melamine has an expanded intergallery spacing compared with both montmorillonite that is modified with melamine hydrochloride or sodium ions alone. The result is consistent association/entrapment of the neutral melamine with the clay during ion exchange.
  • the collected modified clay was re-dispersed into de-ionized water (150L) and allowed to stir for 1 hour at 60° C. before an aqueous solution (10 L) containing 0.385 Kg melamine and 0.26 L HCl (9.65M) at approx 85° C. was added. At this point the mixture was stirred for a further two hours before it was filtered. Next the modified clay was re-dispersed into de-ionized water (150L) and stirred for a further 1 hour at 60° C. prior to filtration, drying and grinding of the modified clay to a particle size less than 50 micron.
  • the collected modified clay was re-dispersed into de-ionized water (150L) and allowed to stir for 1 hour at 60° C. before an aqueous solution (25L) containing 1.925 Kg melamine and 1.3 L HCl (9.65M) at approx 85° C. was added. At this point the mixture was stirred for a further two hours before it was filtered. Next the modified clay was re-dispersed into de-ionized water (200L) and stirred for a further 1 hour at 60° C. prior to filtration, drying and grinding of the modified clay to a particle size less than 50 micron.
  • Results illustrate the robustness of the modification procedure to variation in reaction conditions employed to carry out the modification procedure. This result is consistent with association/entrapment of the neutral melamine molecules with the clay during ion exchange.
  • Results from Example 3 indicate that the intergallery spacing of montmorillonite is expanded further when exchanged with melamine cyanurate ion compared with sodium ion or melamine ion modified montmorillonite alone (Example 1) due to its larger size and hence steric impact.
  • Melamine monohydrochloride salt (1.4 mmol/100 g montmorillonite) and melamine (1.4 mmol/100 g montmorillonite) was then added to the solution and the resultant suspension continued stirring for a further 150 min. Following filtration of the suspension, the precipitate was thoroughly washed with warm distilled water and then preliminary dried under vacuum (75° C.).
  • the resultant granular organically modified clay was ground to a particle size of less than 45 micron and then further dried at 60-80° C. prior to processing or analysis.
  • Example 4 The results from Example 4 indicate that the intergallery spacing of montmorillonite exchanged with melamine cyanurate ion in the presence of melamine and melamine cyanurate is larger than both sodium ion or melamine cyanurate ion exchanged montmorillonite alone (Example 3). This result is consistent with association/entrapment of the neutral melamine and melamine cyanurate with the clay during ion exchange.
  • Melamine monohydrochloride salt (1.4 mmol/100 g montmorillonite) and trimethylcetylammoniun chloride (1.4 mmol/100 g montmorillonite) was then added to the solution and the resultant suspension allowed to cool with continued stirring for a further 150 min. Following filtration of the suspension, the precipitate was thoroughly washed with warm distilled water and then preliminary dried under vacuum (75° C.).
  • the resultant granular organically modified clay was ground to a particle size of less than 45 micron and then further dried at 60-80° C. prior to processing or analysis.
  • Trimethylcetylammonium chloride 1.84 nm
  • Melamine and Trimethylcetylammonium chloride 1.68 nm modified montmorillonite
  • Example 5 The results from Example 5 indicate that the intergallery spacing of montmorillonite exchanged with both trimethylcetylammonium chloride and melamine hydrochloride is larger than sodium but smaller than trimethylcetylammonium ion exchanged montmorillonite. This result is consistent with trimethylcetylammonium chloride and melamine hydrochloride being present in the intergallery spacing of the modified montmorillonite.
  • Hectorite clay (Synthetic Laponite RD) was modified using the same general procedure as employed in Example 2 taking into consideration its lower cation exchange capacity (CEC) of 55 mmol/100 g and employing a 1% solution for modification. Strict control was placed over the mole ratio of hectorite CEC and melamine salt to encourage platelet agglomeration. Following treatment with the melamine salt/melamine, the modified synthetic clay was separated from the treatment solution by filtration.
  • Example 6 The results from Example 6 indicate that the intergallery spacing of synthetic hectorite exchanged with melamine hydrochloride in the presence of melamine is larger than sodium changed montmorillonite.
  • nylon12 While each of the following examples use Nylon12, Nylon6 or Nylon66 as the polyamide based matrix, the person skilled in the art will appreciate that the examples for fire retarding nylon12, nylon6 and nylon66 are also applicable to other types of polyamides, polyamide co-polymers, polyamide blends, alloys and the like.
  • Nylon 12 is not affected by the melt dispersion of commercially available ‘organoclay’ at least partially on a nanometer scale (XRD).
  • XRD nanometer scale
  • Nylon 12 is not effected by the melt dispersion of commercially available ‘organoclay’ at least partially on a nanometer scale (XRD) and flame retardant.
  • This dispersion results in improved mechanical performance reduced heat release results via cone calorimetry and vertical burn performance for specimens greater than 1.6 mm thickness compared with conventionally flame retarded nylon12.
  • samples of 0.75 mm thickness provide good smoke and toxic gas release results they fail FAA type 12 sec vertical burn testing and perform badly in radiant panel tests. This indicates that the strategy is not satisfactory to meet the performance of thin parts to the performance requirements of governing bodies such as the FAA.
  • Results indicate the robustness of the formulation in terms of mechanical and fire performance to different processing conditions such as through-put, temperature profile, screw speed for the given screw and barrel configuration provided in FIG. 1 .
  • Results indicate that preferably more than 10% melamine cyanurate is required to pass FAA 12 s vertical burn test requirements at 0.75 mm thickness. Results also indicate that unlike classically flame retarded nylon12 this fire performance is achievable whilst maintaining excellent mechanical properties relative to nylon12. TABLE 22 Performance of Formulations incorporating different concentrations of IOH2 and Melamine cyanurate Tensile Tensile Notched FAA 12 s Vertical Modulus Strength Impact burn (0.75 mm) Formulation (MPa) (MPa) Strength (J/m 2 ) Ext.
  • Example 21 Illustrates the Mechanical and 12s Vertical Burn Performance (Table 25) and Cone Calorimetry Results (Table 26) of Nylon12 Formulations Prepared with IOH2 (Example 2), Melamine Cyanurate and Magnesium Hydroxide.
  • Table 27 provides Radiant Panel, Smoke, and 60s FAA Type Vertical Burn Results for the Above Mentioned Formulations.
  • Mechanical and Vertical Burn Performance of Nylon 12 Formulations Incorporating IOH2, Melamine Cyanurate and Magnesium Hydroxide of Different Surface Functionality and Particle Size Distribution is Provided in Table 28.
  • Results from Example 14 show that excellent processability, mechanical, vertical burn, and heat release results are obtainable with formulations incorporating IOH2, melamine cyanurate and low concentrations of magnesium hydroxide in particular formulations incorporating IOH dispersed at least partially on a nanometre scale, melamine cyanurate and 2.5% magnesium hydroxide which provides excellent mechanical, vertical burn and peak and average heat release results.
  • the results also indicate that Mg(OH 2 ) of different grades may be employed in conjunction with IOH2 and melamine cyanurate to produce formulations with excellent processability, mechanical and fire performance.
  • TABLE 25 Mechanical Performance of nylon materials with various amounts of IOH2 and conventional flame retardants Notched FAA 12 s Tensile Tensile Impact Vertical burn MFI Modulus Strength Strength Ext.
  • Example 29 Illustrates the Mechanical and Vertical Burn Performance (Table 29) of Nylon12 Formulations Prepared with the Inorganic-Organic Hybrids Outlined in Examples 1, 2 & 4 and Melamine Cyanurate
  • Example 6 shows the XRD of Nylon12 Formulations Incorporating Modified and Intercalated Hectorite (Example 6) Dispersed at Least Partially on a Nanometre Scale (FIG. 5 ) and Melamine Cyanurate and the Formulations Vertical Burn Performance (Table 31)
  • FIG. 6 provides examples of components manufactured by rotational moulding employing formulations incorporating IOH2, melamine cyanurate optionally magnesium hydroxide and other additives such as but not limited to formulation 13 and 34.
  • formulations incorporating IOH2, melamine cyanurate optionally magnesium hydroxide and other additives such as but not limited to formulation 13 and 34.
  • the examples illustrate that such formulations show suitable thermal/oxidative stability and melt rheology for manufacturing components under low shear and thermally demanding environments.

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US20070290410A1 (en) * 2005-07-29 2007-12-20 Koo Joseph H Fire retardant polymer nanocomposites for laser sintering
US20080302733A1 (en) * 2007-06-05 2008-12-11 Amcol International Corporation Coupling agent-reacted mercury removal media
US20090136744A1 (en) * 2007-10-19 2009-05-28 Saint-Gobain Ceramics & Plastics, Inc. Applications of shaped nano alumina hydrate as barrier property enhancer in polymers
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US20100151160A1 (en) * 2008-12-17 2010-06-17 Saint-Gobain Ceramics & Plastics, Inc. Applications of shaped nano alumina hydrate in inkjet paper
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US7828399B1 (en) 2008-03-03 2010-11-09 Partition System Inc. Universal locker system
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US10332222B1 (en) 2017-12-02 2019-06-25 M-Fire Supression, Inc. Just-in-time factory methods, system and network for prefabricating class-A fire-protected wood-framed buildings and components used to construct the same
US10430757B2 (en) 2017-12-02 2019-10-01 N-Fire Suppression, Inc. Mass timber building factory system for producing prefabricated class-A fire-protected mass timber building components for use in constructing prefabricated class-A fire-protected mass timber buildings
US10653904B2 (en) 2017-12-02 2020-05-19 M-Fire Holdings, Llc Methods of suppressing wild fires raging across regions of land in the direction of prevailing winds by forming anti-fire (AF) chemical fire-breaking systems using environmentally clean anti-fire (AF) liquid spray applied using GPS-tracking techniques
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US20210171737A1 (en) * 2019-10-10 2021-06-10 Kyung Dong One Corporation Highly Flame-Retardant Organically Modified Nanoparticle, Organic-Inorganic Composite Synthetic Resin Containing the Same and Processed Product Thereof
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US11836807B2 (en) 2017-12-02 2023-12-05 Mighty Fire Breaker Llc System, network and methods for estimating and recording quantities of carbon securely stored in class-A fire-protected wood-framed and mass-timber buildings on construction job-sites, and class-A fire-protected wood-framed and mass timber components in factory environments
US11865394B2 (en) 2017-12-03 2024-01-09 Mighty Fire Breaker Llc Environmentally-clean biodegradable water-based concentrates for producing fire inhibiting and fire extinguishing liquids for fighting class A and class B fires
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CN117720783A (zh) * 2023-12-22 2024-03-19 江苏馨德高分子材料股份有限公司 一种无卤膨胀型阻燃电缆料及其制备工艺

Families Citing this family (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8420040B2 (en) * 2004-08-27 2013-04-16 National Institute For Materials Science Organic-inorganic composite and polymeric composite material, and method producing them
JP5248105B2 (ja) * 2007-03-30 2013-07-31 シーシーアイ株式会社 層間化合物及びその製造方法
DE102009038518B4 (de) * 2008-08-29 2015-04-30 Bene_Fit Systems Gmbh & Co. Kg Verwendung einer Zusammensetzung zur Reduzierung des Formaldehydgehaltes in Holzwerkstoffen, Verfahren zur Herstellung eines formaldehydreduzierten Holzwerkstoffs
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MX354161B (es) 2011-09-07 2018-02-14 Nanto Cleantech S R L Nanoarcillas que contienen productos quimicos ignifugos para aplicaciones de ingifugacion.
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CN103073515B (zh) * 2012-12-03 2015-01-07 杭州捷尔思阻燃化工有限公司 一种大粒径三聚氰胺氰尿酸盐及其制备方法和应用
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WO2015024487A1 (en) * 2013-08-23 2015-02-26 Rhodia Operations Flame retardant prepared from amide derivatives and process for making the same
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US9517372B2 (en) 2013-11-18 2016-12-13 Heat Shield, Inc Bentonite-fiberglass fire blanket
JP6216461B2 (ja) * 2013-12-10 2017-10-18 コリア インスティテュート オブ コンストラクション テクノロジー 熱発泡性塗布剤及びその製造方法
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WO2016154137A1 (en) * 2015-03-20 2016-09-29 The Texas A&M University System Reactive coating method for deposition of insoluble flame retardant using a water-borne coating procedure
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RU2641931C1 (ru) * 2016-12-20 2018-01-23 Федеральное государственное бюджетное образовательное учреждение высшего образования "Волгоградский государственный технический университет" (ВолгГТУ) Фторсодержащая полиамидная композиция с пониженной горючестью
US11661497B2 (en) * 2017-04-07 2023-05-30 Imerys Usa, Inc. Flame-retardant polymer composition
US10710348B2 (en) 2017-07-26 2020-07-14 The Boeing Company Methods and apparatus to increase fire resistance and fracture toughness of a composite structure
CN108410014A (zh) * 2018-01-15 2018-08-17 大连亚泰科技新材料股份有限公司 一种蒙脱土/氢氧化镁复合阻燃材料及制备方法
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CN109354862A (zh) * 2018-09-04 2019-02-19 徐州市华天塑业有限公司 一种高导热尼龙材料及其制备方法
CN109467715B (zh) * 2018-12-11 2021-05-18 辽宁工程技术大学 一种磷酸钴无机有机杂化材料的合成方法
NO346733B1 (en) 2019-06-28 2022-12-05 Klingelberg Products As Flame retardant, method for its preparation and article comprising same
CN110343413B (zh) * 2019-07-17 2021-01-08 烟台大学 氮磷膨胀型阻燃剂及在水性聚氨酯涂料应用的制备方法
CN114391033A (zh) 2019-09-06 2022-04-22 科思创(荷兰)有限公司 基于阻燃聚酰胺的3d打印挤出材料
CN113045892B (zh) * 2019-12-28 2022-06-28 合肥杰事杰新材料股份有限公司 一种阻燃尼龙66材料及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4889885A (en) * 1987-03-04 1989-12-26 Kabushiki Kaisha Toyota Chuo Kenkyusho Composite material containing a layered silicate
US5770644A (en) * 1996-02-26 1998-06-23 Mitsubishi Engineering Plastics Corporation Fire retardent polyester resin composition and process for producing the same
US6323272B1 (en) * 1999-08-13 2001-11-27 Ems-Chemie Ag Polyamide resin composition
US6355717B1 (en) * 1999-08-04 2002-03-12 Ems-Chemie Ag Layered silicate-containing composite resin composition, and moulded barrier composite resin
US20030209699A1 (en) * 1999-08-06 2003-11-13 Chyall Leonard J. Intumescent polymer compositions

Family Cites Families (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1114174A (en) 1964-12-18 1968-05-15 Berk Ltd Synthetic thermoplastic polymer composition
US4341694A (en) * 1981-07-06 1982-07-27 Borg-Warner Corporation Intumescent flame retardant compositions
US4511684A (en) 1982-12-15 1985-04-16 Ems-Inventa Ag Flame retardant polyamides and agent for inducing flame retardancy
US4739007A (en) 1985-09-30 1988-04-19 Kabushiki Kaisha Toyota Chou Kenkyusho Composite material and process for manufacturing same
JPH04357107A (ja) * 1991-03-29 1992-12-10 Nippon Paint Co Ltd シリコーン油インターカレート組成物
WO1993004118A1 (en) 1991-08-12 1993-03-04 Allied-Signal Inc. Melt process formation of polymer nanocomposite of exfoliated layered material
CA2115255A1 (en) * 1991-08-12 1993-03-04 Macrae Maxfield Melt process formation of polymer nanocomposite of exfoliated layered material
US5753003A (en) * 1993-02-16 1998-05-19 Canon Kabushiki Kaisha Method for bio-remedying polluted soil
JPH07242817A (ja) * 1994-03-04 1995-09-19 Showa Denko Kk ポリアミド樹脂組成物
JPH08319418A (ja) * 1995-05-29 1996-12-03 Showa Denko Kk 難燃性ポリアミド樹脂組成物
US5708065A (en) * 1995-12-22 1998-01-13 E. I. Du Pont De Nemours And Company Fire resistant resin compositions
JPH09227119A (ja) * 1996-02-22 1997-09-02 Nippon Paint Co Ltd メラミン樹脂含有有機粘土複合体、及びそれを含む水性塗料組成物
JP3992120B2 (ja) * 1996-07-17 2007-10-17 エムスケミー・ジャパン株式会社 珪酸塩トリアジン複合体及びそれを含有する難燃性樹脂複合体
JPH10182141A (ja) * 1996-12-24 1998-07-07 Sumitomo Bakelite Co Ltd 熱膨張性材料及びそれを含む難燃性樹脂組成物
WO1998036022A1 (de) 1997-02-17 1998-08-20 Basf Aktiengesellschaft Flammgeschützte thermoplastische formmassen
US5773502A (en) 1997-10-14 1998-06-30 General Electric Company Fire retardant blends
CN1301278A (zh) 1998-02-13 2001-06-27 索罗蒂亚公司 聚合物纳米复合材料组合物
WO1999043747A1 (en) 1998-02-27 1999-09-02 General Electric Company Flame retardant polymer blends
JP2000053858A (ja) 1998-08-07 2000-02-22 Showa Denko Kk 高剛性難燃ポリアミド複合材料
CN1322057C (zh) * 1998-07-30 2007-06-20 东丽株式会社 聚酰胺树脂组合物及其制造方法
EP1165438A1 (de) * 1999-01-28 2002-01-02 Vantico AG Melamin-modifizierte schichtsilikate
CA2371300C (en) 1999-04-30 2011-04-05 Alcan International Limited Fire retardant compositions
JP2001049117A (ja) * 1999-08-13 2001-02-20 Emusu Showa Denko:Kk ポリアミド系樹脂組成物
US6610770B1 (en) * 1999-10-04 2003-08-26 Elementis Specialties, Inc. Organoclay/polymer compositions with flame retardant properties
JP2001118428A (ja) * 1999-10-19 2001-04-27 Emusu Showa Denko:Kk 電線被覆用樹脂組成物
WO2002016479A1 (fr) * 2000-08-25 2002-02-28 Sekisui Chemical Co., Ltd. Produit moule en forme de feuille
CA2431037C (en) * 2000-12-15 2010-05-25 Agrolinz Melamin Gmbh Modified inorganic particles
AU2002952373A0 (en) 2002-10-31 2002-11-14 Commonwealth Scientific And Industrial Research Organisation Fire resistant material

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4889885A (en) * 1987-03-04 1989-12-26 Kabushiki Kaisha Toyota Chuo Kenkyusho Composite material containing a layered silicate
US5770644A (en) * 1996-02-26 1998-06-23 Mitsubishi Engineering Plastics Corporation Fire retardent polyester resin composition and process for producing the same
US6355717B1 (en) * 1999-08-04 2002-03-12 Ems-Chemie Ag Layered silicate-containing composite resin composition, and moulded barrier composite resin
US20030209699A1 (en) * 1999-08-06 2003-11-13 Chyall Leonard J. Intumescent polymer compositions
US6323272B1 (en) * 1999-08-13 2001-11-27 Ems-Chemie Ag Polyamide resin composition

Cited By (54)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9745515B2 (en) 2002-10-31 2017-08-29 Commonwealth Scientific And Industrial Research Organisation Fire resistant material
US20070290410A1 (en) * 2005-07-29 2007-12-20 Koo Joseph H Fire retardant polymer nanocomposites for laser sintering
US20080302733A1 (en) * 2007-06-05 2008-12-11 Amcol International Corporation Coupling agent-reacted mercury removal media
US8382990B2 (en) 2007-06-05 2013-02-26 Amcol International Corporation Method of removing mercury and/or arsenic from water or mercury from a gas using an extruded onium ion intercalated silane coupling agent reacted layered phyllosilicate
US8575255B2 (en) * 2007-10-19 2013-11-05 Saint-Gobain Ceramics & Plastics, Inc. Applications of shaped nano alumina hydrate as barrier property enhancer in polymers
US20090136744A1 (en) * 2007-10-19 2009-05-28 Saint-Gobain Ceramics & Plastics, Inc. Applications of shaped nano alumina hydrate as barrier property enhancer in polymers
US7828399B1 (en) 2008-03-03 2010-11-09 Partition System Inc. Universal locker system
WO2009137230A1 (en) * 2008-05-07 2009-11-12 Amcol International Corporation Coupling agent-reacted mercury and/or arsenic ion removal media
GB2461172A (en) * 2008-06-24 2009-12-30 Univ Chung Yuan Christian A modified clay for use in a fire retardant polymer composite
DE102009030248B4 (de) 2008-06-24 2020-07-09 Chung Yuan Christian University Modifizierter Ton und Ton-Polymer-Komposit
US8460768B2 (en) 2008-12-17 2013-06-11 Saint-Gobain Ceramics & Plastics, Inc. Applications of shaped nano alumina hydrate in inkjet paper
US8686073B2 (en) 2008-12-17 2014-04-01 Basf Se Layered silicate flame retardant compositions
WO2010069835A1 (en) * 2008-12-17 2010-06-24 Basf Se Layered silicate flame retardant compositions
US20100151160A1 (en) * 2008-12-17 2010-06-17 Saint-Gobain Ceramics & Plastics, Inc. Applications of shaped nano alumina hydrate in inkjet paper
CN102321487A (zh) * 2011-06-24 2012-01-18 苏州科技学院 一种纳米复合膨胀型阻燃剂及其制备方法
US10385479B2 (en) * 2015-02-09 2019-08-20 Brookwood Companies Incorporated Fire retardant nylon fibers and methods for making them
WO2016130534A1 (en) * 2015-02-09 2016-08-18 Brookwood Companies Incorporated Fire retardant nylon fibers and methods for making them
US12018406B2 (en) 2015-02-09 2024-06-25 Brookwood Companies Incorporated Fire retardant nylon fibers and methods for making them
US11447895B2 (en) 2015-02-09 2022-09-20 Brookwood Companies Incorporated Fire retardant nylon fibers and methods for making them
US10883199B2 (en) 2015-02-09 2021-01-05 Brookwood Companies Incorporated Fire retardant nylon fibers and methods for making them
US10899038B2 (en) 2017-12-02 2021-01-26 M-Fire Holdings, Llc Class-A fire-protected wood products inhibiting ignition and spread of fire along class-A fire-protected wood surfaces and development of smoke from such fire
US11794044B2 (en) 2017-12-02 2023-10-24 Mighty Fire Breaker Llc Method of proactively forming and maintaining GPS-tracked and mapped environmentally-clean chemical firebreaks and fire protection zones that inhibit fire ignition and flame spread in the presence of wild fire
US10653904B2 (en) 2017-12-02 2020-05-19 M-Fire Holdings, Llc Methods of suppressing wild fires raging across regions of land in the direction of prevailing winds by forming anti-fire (AF) chemical fire-breaking systems using environmentally clean anti-fire (AF) liquid spray applied using GPS-tracking techniques
US10332222B1 (en) 2017-12-02 2019-06-25 M-Fire Supression, Inc. Just-in-time factory methods, system and network for prefabricating class-A fire-protected wood-framed buildings and components used to construct the same
US10814150B2 (en) 2017-12-02 2020-10-27 M-Fire Holdings Llc Methods of and system networks for wireless management of GPS-tracked spraying systems deployed to spray property and ground surfaces with environmentally-clean wildfire inhibitor to protect and defend against wildfires
US10311444B1 (en) 2017-12-02 2019-06-04 M-Fire Suppression, Inc. Method of providing class-A fire-protection to wood-framed buildings using on-site spraying of clean fire inhibiting chemical liquid on exposed interior wood surfaces of the wood-framed buildings, and mobile computing systems for uploading fire-protection certifications and status information to a central database and remote access thereof by firefighters on job site locations during fire outbreaks on construction sites
US10290004B1 (en) 2017-12-02 2019-05-14 M-Fire Suppression, Inc. Supply chain management system for supplying clean fire inhibiting chemical (CFIC) totes to a network of wood-treating lumber and prefabrication panel factories and wood-framed building construction job sites
US10919178B2 (en) 2017-12-02 2021-02-16 M-Fire Holdings, Llc Class-A fire-protected oriented strand board (OSB) sheathing, and method of and automated factory for producing the same
US10260232B1 (en) 2017-12-02 2019-04-16 M-Fire Supression, Inc. Methods of designing and constructing Class-A fire-protected multi-story wood-framed buildings
US11836807B2 (en) 2017-12-02 2023-12-05 Mighty Fire Breaker Llc System, network and methods for estimating and recording quantities of carbon securely stored in class-A fire-protected wood-framed and mass-timber buildings on construction job-sites, and class-A fire-protected wood-framed and mass timber components in factory environments
US11395931B2 (en) 2017-12-02 2022-07-26 Mighty Fire Breaker Llc Method of and system network for managing the application of fire and smoke inhibiting compositions on ground surfaces before the incidence of wild-fires, and also thereafter, upon smoldering ambers and ashes to reduce smoke and suppress fire re-ignition
US11400324B2 (en) 2017-12-02 2022-08-02 Mighty Fire Breaker Llc Method of protecting life, property, homes and businesses from wild fire by proactively applying environmentally-clean anti-fire (AF) chemical liquid spray in advance of wild fire arrival and managed using a wireless network with GPS-tracking
US10267034B1 (en) 2017-12-02 2019-04-23 M-Fire Suppression, Inc. On-job-site method of and system for providing class-A fire-protection to wood-framed buildings during construction
US10430757B2 (en) 2017-12-02 2019-10-01 N-Fire Suppression, Inc. Mass timber building factory system for producing prefabricated class-A fire-protected mass timber building components for use in constructing prefabricated class-A fire-protected mass timber buildings
US11730987B2 (en) 2017-12-02 2023-08-22 Mighty Fire Breaker Llc GPS tracking and mapping wildfire defense system network for proactively defending homes and neighborhoods against threat of wild fire by spraying environmentally-safe anti-fire chemical liquid on property surfaces to inhibit fire ignition and flame spread in the presence of wild fire
US11633636B2 (en) 2017-12-02 2023-04-25 Mighty Fire Breaker Llc Wireless neighborhood wildfire defense system network supporting proactive protection of life and property in a neighborhood through GPS-tracking and mapping of environmentally-clean anti-fire (AF) chemical liquid spray applied to the property before wild fires reach the neighborhood
US11638844B2 (en) 2017-12-02 2023-05-02 Mighty Fire Breaker Llc Method of proactively protecting property from wild fire by spraying environmentally-clean anti-fire chemical liquid on property surfaces prior to wild fire arrival using remote sensing and GPS-tracking and mapping enabled spraying
US11642555B2 (en) 2017-12-02 2023-05-09 Mighty Fire Breaker Llc Wireless wildfire defense system network for proactively defending homes and neighborhoods against wild fires by spraying environmentally-clean anti-fire chemical liquid on property and buildings and forming GPS-tracked and mapped chemical fire breaks about the property
US11654313B2 (en) 2017-12-02 2023-05-23 Mighty Fire Breaker Llc Wireless communication network, GPS-tracked ground-based spraying tanker vehicles and command center configured for proactively spraying environmentally-safe anti-fire chemical liquid on property surfaces to inhibit fire ignition and flame spread in the presence of wild fire
US11654314B2 (en) 2017-12-02 2023-05-23 Mighty Fire Breaker Llc Method of managing the proactive spraying of environment ally-clean anti-fire chemical liquid on GPS-specified property surfaces so as to inhibit fire ignition and flame spread in the presence of wild fire
US11697041B2 (en) 2017-12-02 2023-07-11 Mighty Fire Breaker Llc Method of proactively defending combustible property against fire ignition and flame spread in the presence of wild fire
US11697040B2 (en) 2017-12-02 2023-07-11 Mighty Fire Breaker Llc Wild fire defense system network using a command center, spraying systems and mobile computing systems configured to proactively defend homes and neighborhoods against threat of wild fire by spraying environmentally-safe anti-fire chemical liquid on property surfaces before presence of wild fire
US11697039B2 (en) 2017-12-02 2023-07-11 Mighty Fire Breaker Llc Wireless communication network, GPS-tracked back-pack spraying systems and command center configured for proactively spraying environmentally-safe anti-fire chemical liquid on property surfaces to inhibit fire ignition and flame spread in the presence of wild fire
US11707639B2 (en) 2017-12-02 2023-07-25 Mighty Fire Breaker Llc Wireless communication network, GPS-tracked mobile spraying systems, and a command system configured for proactively spraying environmentally-safe anti-fire chemical liquid on combustible property surfaces to protect property against fire ignition and flame spread in the presence of wild fire
US11865394B2 (en) 2017-12-03 2024-01-09 Mighty Fire Breaker Llc Environmentally-clean biodegradable water-based concentrates for producing fire inhibiting and fire extinguishing liquids for fighting class A and class B fires
US11865390B2 (en) 2017-12-03 2024-01-09 Mighty Fire Breaker Llc Environmentally-clean water-based fire inhibiting biochemical compositions, and methods of and apparatus for applying the same to protect property against wildfire
US11826592B2 (en) 2018-01-09 2023-11-28 Mighty Fire Breaker Llc Process of forming strategic chemical-type wildfire breaks on ground surfaces to proactively prevent fire ignition and flame spread, and reduce the production of smoke in the presence of a wild fire
US11530315B2 (en) * 2019-10-10 2022-12-20 Kyung Dong One Corporation Highly flame-retardant organically modified nanoparticle, organic-inorganic composite synthetic resin containing the same and processed product thereof
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CN117070175A (zh) * 2023-09-28 2023-11-17 建滔(广州)电子材料制造有限公司 一种高阻燃的覆铜板用胶黏剂及其制备方法
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JP5731302B2 (ja) 2015-06-10
ATE545690T1 (de) 2012-03-15
BR0315879A (pt) 2005-10-04
EP1576073A4 (en) 2008-06-25
CN1732246A (zh) 2006-02-08
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US9745515B2 (en) 2017-08-29
JP2006504815A (ja) 2006-02-09
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CA2504414C (en) 2013-04-09
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CA2504414A1 (en) 2004-05-13
US20110281981A1 (en) 2011-11-17

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