WO2003093395A1 - Nouveaux materiaux resistants au feu et procede de production associe - Google Patents

Nouveaux materiaux resistants au feu et procede de production associe Download PDF

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WO2003093395A1
WO2003093395A1 PCT/US2003/013433 US0313433W WO03093395A1 WO 2003093395 A1 WO2003093395 A1 WO 2003093395A1 US 0313433 W US0313433 W US 0313433W WO 03093395 A1 WO03093395 A1 WO 03093395A1
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fire retardant
cellulose
solution
diammonium
retardant composition
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PCT/US2003/013433
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English (en)
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William H. Jones
H. Dean Bunnell
Allen W. Potter
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Niponi, Llc
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Priority to AU2003234302A priority Critical patent/AU2003234302A1/en
Priority to CA002484327A priority patent/CA2484327A1/fr
Priority to EP03728615A priority patent/EP1499695A1/fr
Publication of WO2003093395A1 publication Critical patent/WO2003093395A1/fr

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    • 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
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03—Polysaccharides or derivatives thereof
    • D06M15/05—Cellulose or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/38—Polysaccharides or derivatives thereof
    • C04B24/383—Cellulose or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B11/00—Preparation of cellulose ethers
    • C08B11/20—Post-etherification treatments of chemical or physical type, e.g. mixed etherification in two steps, including purification
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C08B15/005—Crosslinking of cellulose derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B31/00—Preparation of derivatives of starch
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B31/00—Preparation of derivatives of starch
    • C08B31/003—Crosslinking of starch
    • C08B31/006—Crosslinking of derivatives of starch
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B31/00—Preparation of derivatives of starch
    • C08B31/08—Ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
    • C08G18/6492—Lignin containing materials; Wood resins; Wood tars; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • 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
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03—Polysaccharides or derivatives thereof
    • D06M15/05—Cellulose or derivatives thereof
    • D06M15/09—Cellulose ethers
    • 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
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03—Polysaccharides or derivatives thereof
    • D06M15/11—Starch or derivatives thereof
    • 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
    • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/60—Agents for protection against chemical, physical or biological attack
    • C04B2103/63—Flame-proofing agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0025—Foam properties rigid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • 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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/30—Flame or heat resistance, fire retardancy properties

Definitions

  • the present invention is directed to a novel family of materials that is inherently fire retardant, exhibits endothermic properties when exposed to high temperature and flame, and exhibits antifungal, antibacterial, and antimildew properties.
  • the novel compounds can be used in a multitude of applications, including powder, slurry, coating, spray, film, filler, lubricant, adhesive, textile, plastic additive, and fiber.
  • Cellulose and cellulosic products are considered flammable because they are readily ignited and are rapidly consumed after ignition. This is because cellulose itself is an inherently flammable material. When cellulose is heated to the decomposition temperature, it yields volatile, flammable gases, as well as liquid and tarry products that may also volatize and ignite, leaving a char consisting mainly of carbon. The slow oxidation of this char is responsible for the afterglow.
  • the idea of attempting to impart fire retardancy to cellulose is well known in the art. See, for example, M. Lewin and S. Sell, Technology and Test Methods of Flame Proofing of Cellulosics, Flame-Retardant Polymer Materials. 19-136 (1975), the entirety of which is incorporated by reference herein.
  • Fire retardant compositions can be classified into three types: (1) non-durable fire retardants that are easily removed by water, humidity, rain, or perspiration; (2) semi- durable treatments that resist leaching, but lose their effectiveness after a limited number of launderings, or exposure to surfactants or the elements; and (3) durable fire-retardant finishes that withstand leaching, laundering and dry-cleaning.
  • Polymer-clay, polymer-zeolite and polymer-graphite nanocomposites have also generated a great deal of interest lately due to improved thermal and mechanical properties at the same time, a key advantage over existing condensed phase retardant.
  • this type of composite, with well-dispersed intercalated nanocomposite is very difficult to achieve and only applicable to a very limited number of polymers under very difficult processing conditions.
  • the present invention describes the ideal fire retardant cellulose, namely a stable and durable cellulosic material suitable for a broad spectrum of uses, with intrinsic, long-lasting, and significant flame retardant properties, which can be manufactured inexpensively and with minimal environmental concerns.
  • the invention disclosed herein is also applicable to molecules related to cellulose, including other polysaccharides such as starch, and petroleum based polymers.
  • the novel chemical processing and cross-linking has broad application to a wide variety of compounds, as disclosed herein.
  • the subject invention achieves an inherently fire retardant material, not through treating it or coating it, but through a chemical reaction and cross-linking mechanism that imparts fire retardancy into the cross-linked materials as a property of the material itself.
  • the family of materials to be reacted and cross-linked includes polysaccharides (such as cellulose, starch), petrochemicals, and novel composites containing those fire retardant materials.
  • the cross-linked materials have a stable shelf-life (i.e., little deterioration of fire resistant properties), are essentially non-toxic when charred, have sufficient adhesiveness, and are malleable. The materials' inherent fire retardancy characteristics do not significantly degrade over time, or exposure to the elements.
  • the cross-linked cellulose, starch and hydrocarbon materials are manufactured with inexpensive base materials, and their manufacture or use do not create environmental problems or concerns.
  • the fire-resistant cellulose molecule is thermally stable and has been shown not to ignite at or higher than 3,500°F.
  • the subject invention comprises inherently fire retardant natural and synthetic polymers including polysaccharides, such as cellulose or starch, and petrochemicals. Each is discussed separately below.
  • the basic reaction involves a polymerization with cross-linking of natural and synthetic polymers containing hydroxyl groups, through use of a cross-linking agent (e.g., a diammonium salt, such as diammonium phosphate (DAP)).
  • a cross-linking agent e.g., a diammonium salt, such as diammonium phosphate (DAP)
  • DAP diammonium phosphate
  • the material to be reacted is treated so that it contains ammonia groups.
  • the sites of the ammonia groups are then linked together with the diammonium salt.
  • the salt is DAP
  • the reaction forms a cross-linker containing a phosphate group.
  • water molecules are entrapped in the resulting cross-linked material that contribute to the endothermic characteristics of the material.
  • the process of the invention produces a cross-linked fire retardant polymeric product.
  • This product exhibits fire retardant properties that are above and beyond those produced by a simple mixture or blend of the reactants used.
  • a cross- linking agent e.g. diammonium phosphate or diammonium sulfate
  • X P, S, etc.
  • preferred cross-linking agents are inorganic ammonium salts containing at least two ammonium groups per molecule.
  • Some examples include diammonium phosphate, diammonium sulfate, diammonium chromate, and diammonium borate of which diammonium phosphate is presently preferred.
  • An alternative explanation of the cross-linked results is that the cross-linking moiety consists primarily of phosphorus and oxygen atoms. In the latter case, it would be expected that cross-linking agents containing phosphorus and oxygen (phosphates) other than diammonium phosphate would also produce acceptable fire retardant compositions.
  • the cross-linking agent useful in the present invention in its broadest scope can be an inorganic ammonium salt, a phosphate, or both (e.g. diammonium phosphate).
  • the critical feature of this cross-linking agent is that it is capable of cross-linking or reacting with the natural or synthetic polymer containing branched hydroxyl groups to produce a fire retardant composition that is more fire retardant that a simple mixture or blend of the polymer with the cross-linking agent (an inorganic ammonium salt or a phosphate).
  • the preferred phosphate useful as the cross-linking agent or reactant in the invention is diammonium phosphate.
  • any phosphate capable of cross-linking or reacting with a natural or synthetic polymer containing branched hydroxyl groups to produce a fire retardant composition that is more fire retardant that a simple mixture or blend of the polymer with the phosphate is acceptable.
  • Such phosphates are generally selected from inorganic, non-metallic phosphates such as the magnesium phosphates, ammonium phosphates, calcium phosphates, sodium phosphates, potassium phosphates and the like.
  • cross-linked hydroxy ethyl cellulose or the equivalent (as referenced below), has been discovered in which the cross-linlcer contains at least two ammonia groups as the reactive sites of the cross-linker (or other cross-linkers as discussed below). In a preferred embodiment of the invention, at least two of the ammonia groups contained in the cross-linker are bound to a phosphate group.
  • the resulting fire retardant cellulosic material has unique characteristics as measured by nuclear magnetic resonance, infrared spectroscopy, and mass spectroscopy.
  • the term cellulose refers generally to a polymerized glucose made up of beta glucosidic bonds.
  • the cellulose is preferably hydroxy ethyl cellulose, but may also be hydroxy propyl cellulose, hydroxy isopropyl cellulose, and/or combinations thereof. I ⁇ addition, cellulose having hydroxy butyl groups, hydroxy pentyl groups and/or longer carbonyl groups may be used and are considered as likely chemical structures to be used in the present invention. In its broadest scope, any cellulosic material capable of cross-linking with the type of cross- linker disclosed herein may be used.
  • fire resistant is synonymous with flame retardance and flame resistance, and generally refers to a material that self extinguishes when exposed to a source of flame.
  • the fire-retardant cellulose polymer in its solid form, has a varying solubility in water that is related in part to its molecular length and the degree of cross-linking.
  • the degree of cross-linking and average molecular chain length may be varied by the reaction conditions (e.g., the temperature used in the reaction process) as well as by the characteristics of the starting cellulosic material. Centrifuge technology, distillation, and fractionation techniques can be used for separation of the fire retardant cellulosic polymer chain lengths.
  • the cellulose chars but does not combust.
  • the cross-linked ammonia groups appear to prevent oxygen from igniting the cellulose molecule.
  • vapor is also generated when the cellulose product is contacted with an ignition source. It is postulated that the disclosed cross-linking mechanism traps water within the cellulose polymer. Finally, a cross-link which includes either phosphates or sulfates may further increase the fire retardancy of the compound.
  • THERMOLOSETM refers to the novel material made by practicing the invention that is available from Thermolose Technologies, Inc., 1981 Pine Hall Drive, State College, Pennsylvania 16803. The following three examples describe the basic synthesis of the fire resistant cellulose. Example 1
  • Example 2 About 19.2 grams of hydroxy ethyl cellulose powder was added to about 1,200 ml water, resulting in a solution containing about 10% hydroxy ethyl cellulose. The solution was then heated to about 60-70°C. Approximately 320 ml of liquid ammonia was mixed into the solution. Approximately 32 grams of solid diammonium phosphate was then added to the solution. The temperature of the solution was increased to approximately 90°C for about 10 to 15 minutes, resulting in a thick, viscous liquid.
  • Example 2 About 4.8 grams of hydroxy ethyl cellulose powder was added to about 80 ml of liquid ammonia at approximately room temperature. The resulting solution was stirred for about 30-45 minutes. Eight (8) grams of diammonium phosphate was then added and stirred into the solution until a clear solution was obtained. The solution was allowed to cross-link for about 24 hours, resulting in a more viscous solution than that obtained according to Example 1.
  • Example 3 Example 3
  • hydroxy ethyl cellulose powder was added to approximately 80 ml of liquid ammonia at approximately room temperature. The solution was then heated to approximately 60-70°C and was stirred for about 30-45 minutes. Eight (8) grams of diammonium phosphate was then added and stirred into the solution until a clear solution was obtained. The temperature of the solution was increased to approximately 60-70°C and then to approximately 90°C for 10-15 minutes. The solution cross-linked, resulting in a viscous solution.
  • HEC hydroxyethyl cellulose
  • the temperature of the solution was then raised to approximately 93 °C.
  • the solution effervesced for several minutes as the reaction occurred. After the effervescing subsided, the solution temperature was reduced to approximately 85°C and held at that temperature to allow free ammonia to escape from the reacted solution.
  • the reacted solution was then allowed to cool to room temperature and was then placed in a suitable container for storage.
  • the resultant solution contained approximately 12 to 15% fire retardant cellulose polymer in water.
  • HEC materials have been utilized in this process.
  • the HEC types are as follows: phannaceutical grade HEC, HEC treated with glyoxal as a wetting agent, hydrophobically modified HEC, HEC containing biostabilizers and various molecular weights of HEC.
  • Example 5 phannaceutical grade HEC, HEC treated with glyoxal as a wetting agent, hydrophobically modified HEC, HEC containing biostabilizers and various molecular weights of HEC.
  • pre-compounding refers to the method of combining all constituents of a solution at the outset of the reaction.
  • Three hundred (300) ml of pure water was placed in a suitable container along with 9.6 grams of hydroxyethyl cellulose (HEC), 75 ml of a 5% ammonia solution, and approximately 78 ml of diammonium phosphate solution (0.16 g/1).
  • HEC hydroxyethyl cellulose
  • 75 ml of a 5% ammonia solution 75 ml of a 5% ammonia solution
  • approximately 78 ml of diammonium phosphate solution (0.16 g/1).
  • the pre-compounded mixture was reacted by raising the temperature of the pre-compounded solution to approximately 93°C.
  • the solution then effervesced for several minutes. After the effervescing subsided, the solution temperature was reduced to approximately 85°C and held at that temperature to allow free ammonia to escape from the reacted solution.
  • the reacted solution was then allowed to cool to room temperature and placed in a suitable container for storage.
  • the resultant solution contained approximately 12 to 15% fire retardant cellulose polymer in water.
  • the resulting mixture can immediately be stored in a suitable container. It must be noted that the mixture may contain a noticeable amount of ammonia. This residual ammonia can be allowed to outgas naturally by leaving the container uncovered under an exhaust hood or the ammonia can be removed at a later time by heating the mixture to approximately 80°C until the residual ammonia has been removed.
  • the reacted material should be allowed to cool at a normal rate. Accelerated cooling may cause the reacted polymer solution to separate into multiple phases. Depending on the conditions, these phases may or may not recombine. Boiling the mixture should be avoided. Boiling may break up or fragment the cellulose polymer structure.
  • HEC HEC
  • HEC pharaiaceutical grade HEC
  • HEC treated with glyoxal as a wetting agent hydrophobically modified HEC
  • HEC containing biostabilizers various molecular weights.
  • the reaction time for producing the 4X concentration can be shortened by mixing the HEC and standard ammonia in a suitable container and allowing the mixture to stand covered several hours. This will allow the HEC to dissolve into the ammonia. This pre- staged mixture can then be stored and reacted at a later time. This method significantly reduces processing time over that of previous examples.
  • the water normally added in the standard 4X process can be added to this start solution to reduce viscosity.
  • HEC hydroxyethyl cellulose
  • the vessel containing the paste was then placed into a larger vessel containing water heated to approximately 95°C. As the temperature of the paste reached approximately 93-95°C, the paste effervesced, thus out gassing ammonia achieving the desired reaction. The paste mixture was held at this temperature until the outgassing subsided. The resultant cellulose polymer paste was allowed to dry producing a solid form of the fire retardant cellulose polymer.
  • the resulting mixture can immediately be stored in a suitable container. It must be noted that the mixture may contain a noticeable amount of ammonia. This residual ammonia can be allowed to outgas naturally by leaving the container uncovered under an exhaust hood or the ammonia can be removed at a later time by heating the mixture to approximately
  • the reacted material should be allowed to cool at a normal rate. Accelerated cooling may cause the reacted polymer solution to separate into multiple phases. Depending on the conditions, these phases may or may not recombine. Boiling the mixture should be avoided. Boiling may break up or fragment the cellulose polymer structure.
  • the liquid ammonia could be pre-heated prior to adding with the cellulosic solution or the cellulosic solid material.
  • Cellulose powder can be added to liquid ammonia to fonn a solution, and thereafter diammonium phosphate can be added to the solution, thereby forming the cross-linked cellulosic material. It is believed that DAP can be added directly to a heated solution or slurry or cellulose material, wherein dissociated ammonia groups from the
  • DAP serve as a source of ammonia for the reaction. This results in a variety of end products including, but not limited to, polymeric salts of cellulose, phosphoric and phosphrous acids, MAP (monoam onium phosphate), and THERMOLOSETM.
  • MAP monoam onium phosphate
  • THERMOLOSETM As an alternative to creating cross-linking with diammonium phosphate, other diammonium salts may be used, including diammonium sulfate, diammonium chromate or diammonium borate.
  • Many sources of energy may be employed to cross-link the material, including radiant, solar, laser, electrical or electromagnetic.
  • the cellulose could be hydroxy butyl cellulose, and/or a combination of its isomers, or hydroxy pentyl cellulose, and/or a combination of its isomers.
  • the cellulose used can be put into solution, or can be put into a partial solution, with particulates included in the solution.
  • the cellulose can also be added to water as a gel-like solution. None of these processing methodologies changes the underlying basis for the invention in question, namely a cross- linked cellulosic material where the cross-linker contains a minimum of two ammonium groups as its active sites. The ammonia that is out gassed at the time of reaction of the material is suitable for recycling and reuse in the production of the fire retardant cellulose polymer.
  • the fire retardant cellulose polymer has been made using a wide variety of molecular weights of HEC. As molecular weight increases, so does the viscosity of the solution to be reacted. A mixture of reacted cellulose polymers has been mixed into a single solution. The fire retarding effect remains the same. The solubility, flexibility, and residual water content of the resulting solution changes depending on the molecular weights of HEC used to produce the variations of fire retardant cellulose polymer.
  • the cellulose By adding the ammonium groups to a starting material with hydroxyl groups, such as hydroxy ethyl cellulose (or the equivalent) the cellulose reacts and behaves as if it is an ammonium compound. In this way, it can be "tricked” into cross-linking in a manner similar to other compounds containing ammonium groups. In this fashion, nitrogen containing compounds, such as ammonium groups, are incorporated into the cross-linked structure. It is well known that such groups impart such flame retardant properties. In a preferred embodiment of the invention, another well known flame retardant chemical, a phosphate group, is incorporated into the cross-linker. This may be done through use of diammonium phosphate.
  • a phosphate group is incorporated into the cross-linker. This may be done through use of diammonium phosphate.
  • Cross-linkers incorporating sulfur into the cross-link through use of diammonium sulfate have been used; however, the flame retardancy characteristics are not as great.
  • the specific mechanism of cross-linlcing starting materials in this fashion is thought to entrap water molecules within the material which further enhances the fire retardancy characteristics of the cross-linked material.
  • the unique method of this cross-linlcing reaction results in an equally unique material which has significant fire retardancy characteristics.
  • the resultant fire retardant cellulosic polymer also entraps any chemical substitutions of the original phosphate group as described herein, i.e. any other salt, organic and inorganic intermediary group that is attached to the ammonium groups used as the chemical cross-linkers.
  • the Acton patent, No. 4,225,310 discloses a textile finishing process for textiles containing cellulosic fibers. The process results in a textile which has "crease resistant" properties.
  • the three components which are applied to the cellulose substrate bear no relation to the subject reaction materials, and from the nature of the specifications, it appears that the cross- linking described therein occurs by and between components A, B and C, and not of the cellulose itself. More importantly, the final material described therein does not include a cross-linked cellulose which includes ammonium groups as the active sites, or phosphorus containing groups.
  • the Norlander patent, No. 5,536,369 the inventors describe a cross-linked cellulose for use in absorbent sanitary products.
  • cross-linked cellulose discloses a cross-linked cellulose.
  • the cross-linking agent was a UV-sensitive cinnemate group which was used for the purpose of making the cellulose exhibit greater at adhesion properties for surgical implants.
  • This cross-linked cellulose did not include or anticipate a cross-linlcer with ammonium groups as the active sites, or phosphorus containing groups.
  • U.S. Patent No. 5,888,987 describes a method for manufacturing a softer, more comfortable polysaccharized sponge wherein polysaccharides are cross-linked as a result of process where a frozen solution containing the polysaccharides is immersed in a water- miscible organic solvent which contains a cross-linking agent.
  • the patent includes hydroxy ethyl cellulose as one of many soluble alginates, the patent does not specifically define any cross-linking agent when hydroxy ethyl cellulose is used. More importantly, the cross-linlcing reaction described in the patent is only a standard cross- linlcing reaction which is not capable of producing a material sharing properties with the present invention.
  • the patent does not teach nor does it anticipate a crosslink cellulosic material having a nitrogen and phosphorus containing group.
  • Cellulose Material Characteristics Another feature of the subject invention is that the material is highly endothermic, wherein heat is absorbed by the reaction process. This characteristic is evident from the manufacturing process, as described below.
  • the intermediary cellulosic material e.g., cellulose and ammonium hydroxide
  • the temperature of the batch was reduced by approximately 20° F, due in part to the endothermic nature of the cross- linking reaction.
  • this same characteristic contributes to the flame retardant properties of the subject invention, and allows the material to continue to char, without igniting, in temperatures well in excess of 3,500°F.
  • Some materials containing THERMOLOSETM are cool to the touch only seconds after the flame from a propane torch is extinguished.
  • the resulting cross-linked cellulosic material has unique characteristics as measured by nuclear magnetic resonance, infrared spectroscopy, and mass spectroscopy. NMR studies were done to characterize the resultant cellulosic material including
  • THERMOLOSETM has numerous uses, hi addition to the materials' unique flame retardancy, THERMOLOSETM also exhibits superior antifungal, antimold, antimildew, antibacterial and antiviral properties.
  • borax or a borate can be added to the solution to form an insect repellent, which will contribute to enhanced fire retardancy for both external and internal applications.
  • the cross-linked cellulose is extremely versatile. It may be used as a powder, in a slurry, coating, filler, spray, film, lubricant, adhesive, textile, fiber or plastic additive. It may be incorporated into virtually all building materials, including wood, plywood, particle board, duct materials, shingles, ceramics, concrete, gypsum, plastics, grouts, paints, vinyl products, varnishes, insulations and laminates. It can be added as a coating to other building materials, such as glass, fiberglass, plastics, steel, composites and matrix materials. It has broad application to apparel, including children's sleepwear, auto racing clothing, fiberfill, and virtually all fabrics. It may be used in home furnishings, such as curtains, bedding, carpet fibers and furniture.
  • the invention may be used for numerous insulation needs, including buildings, wires, cables, foams, Styrofoam, isocyanate foams, polystyrene, polyurethane, and paper products.
  • the invention may be used in adhesive products such as glues, tapes, caulking, cements and epoxys.
  • It may be used in brake pads, tires, lubricants, greases, antifreezes, transmission fluids, gas, water and sewer pipes, gaskets and seals, art canvas and art preservation, paper products, Christmas tree decorations, fertilizers, forest fire prevention and fighting compounds, fire fighting garments, tools and equipment, camping and outdoor gear, including tents, tarps, sleeping bags, paper products, medical equipment, including shielding for cautery treatment, laser surgery, or any thermal treatment requiring tissue shielding, annor products, and military uniforms, protective garments, and equipment.
  • the fire retardant cellulose polymer can be utilized in a variety of forms including, but not limited to the following: as a material to coat an object; as a component or filler used in a mixture of various materials; and as a component of a blend of materials.
  • a coating material the fire retardant cellulose polymer can be used to coat an object or surface in a variety of ways including, but not limited to, painting onto, spraying onto, foaming onto, or coating by dipping the object or surface to be protected.
  • the polymer can be applied in a pure form or as part of a mixture as in an additive to paint or other coating materials.
  • a variant of use as a coating includes use as a pressure- treating compound to fire retard unsealed wood/wood products.
  • the polymer can also be mixed as a dry form into various materials including, but not limited to, various foam materials — both rigid and flexible, composites such as particleboard and Oriented Strand
  • Blending the fire retardant cellulose polymer results in the best overall performance and durability.
  • the optimal use of the fire retardant cellulose polymer is to incorporate it into or blend it into the material to be protected. Having the polymer become an integral part of the material to be protected provides optimal performance.
  • This technique can include, but is not limited to, casting and extruding both films and threads.
  • the following examples demonstrate the broad application of the novel fire retardant cellulosic materials.
  • THERMOLOSETM 4X solution The samples were removed and weighed wet. The samples were cured for 48 hours under a radiant heat lamp at approximately 150°F and reweighed. All samples were inscribed with a line at the 6" mark, including an untreated control sample. The samples were then suspended in a vertical position for a vertical flame test in a lab hood. At that point, a Bunsen Burner flame was adjusted to approximately 1 1/2" long and the bottom edge of the Bass Wood control sample was exposed %" into the Bunsen Burner flame for one minute. The burner flame was removed and the entire control sample was consumed in flame. The sample was extinguished with a water spray. In addition to the fire damage, the control sample incurred severe smoke damage. Treated sample number 8 was tested in the same manner as described above. When the Bunsen burner was removed a small flame flickered at the very bottom of the sample and self-extinguished in 5 seconds. Flame spread was approximately 4" with very little smoke damage.
  • Fabric samples were used relating to the furniture industry, seeking a solution for new proposed testing guidelines that increase the standard from a one second direct flame test against flashover to a twenty second direct flame test that requires self extinguishing.
  • THERMOLOSETM was "back coated" to the backside of the fabric and tested for flame resistance.
  • the fabric is currently back coated with a latex coating, at the rate of approximately two ounces to five ounces per square yard.
  • the fabric was cut into one square foot pieces, then cut again in half, one half for treatment, the other for an untreated burn sample comparison.
  • the samples were weighed dry.
  • the first sample weighed 24.5 grams dry.
  • THERMOLOSETM was then applied with a brush to the backside.
  • the rate of application was about 40-50 grams of THERMOLOSETM 4X solution.
  • the wet weight of the fabric was 74.1 grams or 49.3 grams of THERMOLOSETM. After curing under a radiant heat lamp for 12 hours, the cured weight was 32.1 or 7.3 grams of
  • a vertical bum test was conducted using a butane flame, applied to the bottom edge of the control sample. Within 3-4 seconds, the flame was self-sustaining and traveled up the middle of the fabric. Within one minute the fabric was consumed in flames.
  • the THERMOLOSETM coated sample described above was then hung and the test duplicated.
  • the THERMOLOSETM sample sustained a flame after six seconds. The flame spread took approximately twice as long to consume the sample.
  • a second sample was treated with two coats of THERMOLOSETM 4X and 12.5 grams of solid back coating resulted.
  • a direct flame test using butane held horizontally to the front of untreated fabric sample was conducted. The fabric would support a flame after 4-5 seconds. The treated sample had two bums self extinguished after holding the flame to the fabric for 20 seconds. Several other bums failed the 20-second test, however, all passed the 17 second mark.
  • a third sample was treated with four coats of THERMOLOSETM 4X solution.
  • the cured weight of the back coating was 22 grams.
  • the horizontal butane bum test was conducted and the sample passed the 20-second test, a 24 second test and a 26 second test. This example shows that THERMOLOSETM slows and retards flame ignition on these fabrics.
  • Samples of Polyurethane resin and Isocynate used in the production of rigid foam were obtained for testing. Forty-five (45) ml of polyurethane resin was poured into a metal pan 8" long, x 3 V" wide, x 2 3/8" high. Forty-five (45) ml of isocynate was poured into the pan. At that time a glass-stirring rod was used for mixing the two ingredients together for approximately 3 minutes. At that time the reaction started and foam began to form. Measurements were taken of the reacting foam and at the high point a temperature of 190°F was recorded. After approximately 10 minutes the reacted control sample was removed from the pan. The reacted control sample measured approximately 8"x 3 3 ⁇ " x 1 V" and was rigid.
  • THERMOLOSETM 4X liquid can affect the density and mechanical properties of the rigid foam. It may create new applications for this density of flame retardant foam.
  • Standard 100% acrylic water based gloss paint was tested for flame retardancy when mixed with THERMOLOSETM.
  • One hundred fifty (150) ml of THERMOLOSETM 4X liquid and 300 ml or 1 :2 ratio of the paint were blended together with a glass-stirring rod.
  • Ordinary single ply cardboard samples were prepared by cutting into small strips approximately 1" X 3". The cardboard samples were used for applying the blended and control paint on each side. The coatings were cured under a radiant heat lamp for several hours. A direct butane flame was applied for 5 seconds to both the coated and uncoated samples. The object of the bum test was to achieve a self-extinguishing flame after the flame source was removed.
  • the untreated cardboard sample burned and consumed completely. The treated sample burned and consumed at a slower rate.
  • the second test was conducted using 150 ml of THERMOLOSETM 4X liquid blended with 150 ml of the Acrylic paint for a 1 :1 ratio.
  • the test was conducted in the same manner as describe above. The treated sample burned at a much slower rate than the untreated sample and almost self-extinguished.
  • the third test was conducted using 300 ml of THERMOLOSETM 4X liquid and 150 ml of Acrylic paint or a 2:1 ratio. The same test was conducted as described above. The flame self extinguished as soon as the flame source was removed. This example shows that THERMOLOSETM can improve the flame resistance of Acrylic paint.
  • the present invention also encompasses a novel family of composite materials, which exhibit fire retardant properties, and the methods for producing said composite materials. More particularly, the invention describes ceramic, metal, fiberglass, glass and/or carbon fiber composites made with the proprietary flame retardant base compounds described herein. It further describes a preferred embodiment of the composite materials, which exhibit endothermic properties when exposed to heat or flame.
  • ceramics, metals, and carbon fiber materials exhibit limited heat absorptive and flame retardant characteristics. When exposing such materials to the effects of high heat or extreme flames, the materials will melt, fail, or otherwise break down or denature. The inability to withstand high temperatures or flame limits the application of such materials in key markets, including military, aerospace, and automotive markets. Many currently available composites seeking to address these issues incorporate environmentally hazardous or dangerous chemicals to impart certain heat resistant or flame retardant characteristics.
  • the subject invention achieves inherently flame retardant composites, not through treating it or coating it, but by blending into the composite material a sufficient quantity of proprietary THERMOLOSETM material.
  • the current invention overcomes the shortcomings and is the only Icnown source of producing fire retardant composites containing the materials disclosed in this application.
  • THERMOLOSETM 4X One hundred twenty-five (125) ml of THERMOLOSETM 4X was put into a beaker. Seventy-five (75) ml by volume of lightweight ceramics was added obtained from Superior Products International II, Kansas City, MO. A 3/16" steel plate and aluminum tape was used to build up retaining walls about ' ⁇ " high on the front side of the plate. The THERMOLOSETM/ceramic mixture was then poured onto the plate and allowed to stand in order to seek its own level. The test plate was then set on a stand with an infrared heat lamp directly under the bottom side of the plate. The sample was exposed to bottom side heat for three hours. It was then removed from heat and let air cure for over 12 hours. The plate was set in a stand in a vertical position.
  • a Wagner heat gun model # HT 3000 rated at 1100°F top temperature was applied over an area 1/16" thick and the backside temperature was measured. At the 15-minute mark, a reading of 320°F was obtained and at the 30-minute mark, the same 320°F reading was recorded.
  • test plate was placed under the lab hood and set up in a vertical position.
  • a Burns-o-matic propane torch was used at approximately 1500°F.
  • the nozzle was positioned 1 V" away from coated surface of test plate. This resulted in a red-hot center with a diameter of approximately 1".
  • the flame area was approximately ".
  • the backside temperature was measured every 5 minutes. Readings were taken on the front, right side, bottom corner 7 V" away from flame every 5 minutes. The results were as follows.
  • the plate was placed up against the front opening of a radiant heat oven and a good seal was secured.
  • the temperature was increased to 200°F and the test began. At each five minute interval, the temperature was raised 200 °F and backside temperature readings were taken. At the 30-minute mark, the temperature was 1200°F.
  • the readings were as follows.
  • starches may also be reacted and cross- linked to impart fire retardant and endothemiic properties.
  • materials which are starch-based, have little to no fire retardancy, due to the chemical structure of basic starch.
  • products with starch-based components including cardboards, textiles, veneer based products, and other similar composite or glued products, have poor fire retardancy.
  • adhesives and starch- based industrial products incorporate environmentally hazardous or dangerous chemicals to impart certain characteristics. Any starch material capable of becoming fire-retardant by reacting with cross-linking agents disclosed herein may be used in the invention.
  • the current invention overcomes the shortcomings and is the only source known to the inventors of producing a fire retardant starch, amylopectin or glycogen.
  • a basic starch unit such as a maltose, is initially reacted with NaOH, sodium hydroxide. The resulting product is then reacted with ethylene oxide. Both of these reactions are conducted using published techniques and conditions well Icnown to one skilled in the art.
  • hydroxyethyl starch e.g, ethylated starch
  • the resulting completely hydrolyzed compound or a partially hydrolyzed compound is then suspended in water or ammonium hydroxide. Where dissolved in water, ammonium is added, either in its hydrous or anhydrous (or gaseous) form.
  • this reaction product is reacted with diammonium phosphate to produce a cross-linked base material, which constitutes a fire retardant starch.
  • the synthesis route described above also works when the base starting material is an amylopectin or a glycogen, both of which are structurally related to starch, and the molecular differences will not significantly impact upon the reaction process described above or the fire retardant properties of the resultant compound.
  • the base polysaccharide By adding the ammonium groups to the base polysaccharide as described herein (or the equivalent) the base polysaccharide reacts and behaves as if it is an ammonium compound. In this way, it can be "tricked” into cross-linking in a manner similar to other compounds containing ammonia groups. In this fashion, nitrogen-containing compounds, such as ammonia groups, are incorporated into the cross-linked structure. It is well known that such groups impart such flame retardant properties. In a preferred embodiment of the invention, another well-known flame retardant chemical, such as a phosphate group, is incorporated into the cross-linlcer. This may be done through use of diammonium phosphate, diammonium sulfate or other diammonium groups.
  • the resultant fire retardant starch, amylopectin or glycogen also entraps any chemical substitutions of the original phosphate group as described in the patent, i.e. any other salt, organic and inorganic intermediary group that is attached to the ammonium groups used as the chemical cross-linkers.
  • the novel starch is suitable to be used in all starch based products, including food grade starch powders, pharmacological grade starch powders, paper grade starch powders, and textile based starch powders.
  • adhesive field it may be used in a wide range of industrial adhesives for applications as diverse as industrial packaging, corrugated products, nappies/diapers, food and consumer packaging, woodworking and furniture, electronics and paper.
  • Industrial uses for these novel starches could include thickeners and texturisers.
  • specialty starches manufactured with the instant invention may be used for earners, binders and disintegrants in tablets and capsules; thickeners for liquid dosage medicines; and pharmaceutical grade dusting powders for surgical gloves. It would also have broad application in papermaking and textile production. It may be used as a coating, an additive, a processing agent, an organic binder, or as a base material in a multitude of specialty starches and related products obvious to one skilled in the art.
  • hydroxyl-ethyl starch or Ethylated Starch (ES)
  • ES Ethylated Starch
  • the ES should be properly hydrated. This may be accomplished by elevating the temperature of the solution to at or near the boiling point of water.
  • the ES can be hydrated either directly or indirectly. Direct hydration involves briefly heating the ES in solution to the boiling point (approximately
  • the solution effervesced for several minutes as the reaction occurred. After the effervescing subsided, the solution temperature was reduced to approximately 85 °C and held at that temperature to allow free ammonia to escape from the reacted solution. The reacted solution was then allowed to cool to room temperature and was then placed in a suitable container for storage. Some ES solids may precipitate to the bottom of the container. Shaking the container will temporarily re- suspend these solids. Direct hydration of the ES prior to reacting the ES will minimize this effect.
  • ES materials have been utilized with this process to produce the desired fire retarded cross-linked starch polymer.
  • the ES types are as follows: 1. Food Grade ES
  • Pre-Compounding a IX Concentration Three hundred (300) ml of pure water was placed in a suitable container along with 10.0 grams of Ethylated Starch (ES), 75 ml of a 5% Ammonia solution, and approximately 78 ml of diammonium phosphate solution (0.16 Kg/1). This mixture was covered and stored for reaction at a later time. Direct hydration of the ES initially prior to pre-compounding will reduce the likelihood of ES precipitation prior to reaction of the pre-compounded mixture. At a later time, the pre-compounded mixture was reacted by raising the temperature of the pre-compounded solution to approximately 95 °C. The solution then effervesced for several minutes as the reaction occurred.
  • ES Ethylated Starch
  • the solution temperature was reduced to approximately 85°C and held at that temperature to allow free ammonia to escape from the reacted solution.
  • the reacted solution was then allowed to cool to room temperature and placed in a suitable container for storage.
  • the resulting mixture can immediately be stored in a suitable container. It must be noted that the mixture may contain a noticeable amount of ammonia. This residual ammonia can be allowed to outgas naturally by leaving the container uncovered under an exhaust hood or the ammonia can be removed at a later time by heating the mixture to approximately 80°C until the residual ammonia has been removed.
  • the solution then effervesced for several minutes. After the effervescing subsided, the temperature of the solution was reduced to approximately 85°C and held at that temperature to allow free ammonia to escape. The reacted starch polymer solution was then allowed to cool to room temperature and placed in a suitable container for storage. Some ES solids may precipitate to the bottom of the container. Direct hydration of the ES prior to reaction of the ES will minimize this effect.
  • ES types are as follows:
  • the reaction time for producing the 4X concentration can be shortened by mixing the ES and standard ammonia in a suitable container and allowing the mixture to stand covered several hours. This pre-staged mixture can then be stored and reacted at a later time. This method significantly reduces processing time.
  • the water normally added in the standard 4X process can be added to this start solution to reduce viscosity. Some ES solids may precipitate to the bottom of the container. Direct hydration of the ES prior to reaction of the ES should minimize this effect.
  • Ethylated Starch Forty (40.0) grams of Ethylated Starch (ES) were placed in an open mixing vessel under an exhaust hood. Fifty (50.0) grams of diammonium phosphate were ground into a talc-like consistency. The ES and the diammonium phosphate were then mixed together to form a well-blended dry mixture. Thirty (30) ml of a 50% Ammonia solution was mixed into the dry mixture. A small amount of pure water, approximately 40 ml, was added to allow the mixture to assume a workable paste like consistency. The wetted mixture was mechanically blended to produce a uniform paste like structure. The vessel containing the paste was then placed into a larger vessel containing water heated to approximately 95°C.
  • ES Ethylated Starch
  • the paste As the temperature of the paste reached approximately 93-95°C, the paste hydrated and effervesced, thus out gassing ammonia achieving the desired reaction.
  • the paste mixture was held at this temperature until the outgassing subsided.
  • the resultant starch polymer paste was allowed to dry producing a solid form of the fire retardant starch polymer.
  • the resulting mixture can immediately be stored in a suitable container. It must be noted that the mixture may contain a noticeable amount of ammonia. This residual ammonia can be allowed to outgas naturally by leaving the container uncovered under an exhaust hood or the ammonia can be removed at a later time by heating the mixture to approximately 80°C until the residual ammonia has been removed.
  • the reacted material should be allowed to cool at a normal rate. Excessive boiling of the mixture should be avoided. Boiling may break up or fragment the starch polymer structure.
  • the fire retardant starch polymer has been made using a wide variety of molecular weights of ES. As molecular weight increases, so does the viscosity of the solution to be reacted. A mixture of reacted Starch polymers has been mixed into a single solution. The fire retarding effect remains the same. The solubility, flexibility, and residual water content of the resulting solution changes depending on the molecular weights of ES used to produce the variations of fire retardant starch polymer.
  • Petrochemical Starting Materials The invention may also be used to cross-link and fire retard petrochemicals, such as polyethylene glycol and other similar poly glycols. Useful petrochemical polymers are those that are capable of reacting with the cross-linking agents disclosed herein. Typically, these will be polymers containing hydroxyl groups that are located on a linear carbon chain length of five or fewer carbons.
  • Example 28 A test strip coated with the cooled solution passed a flame test. The resulting reactant solution separated into two phases. Although the first phase showed negligible flame retardant properties, the second phase exhibited flame retardancy. Example 28

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Abstract

L'invention concerne des compositions résistantes au feu ainsi que leur procédé de fabrication. Pour préparer ces compositions, on fait réagir un polymère naturel ou synthétique contenant des groupes hydroxyle et un catalyseur, tel que de l'hydroxyde d'ammonium, avec un agent de réticulation inorganique qui contient au moins deux groupes ammonium par molécule ou un phosphate inorganique.
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