WO1991000327A1 - Ignifuges et produits les incorporant - Google Patents

Ignifuges et produits les incorporant Download PDF

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Publication number
WO1991000327A1
WO1991000327A1 PCT/US1990/003700 US9003700W WO9100327A1 WO 1991000327 A1 WO1991000327 A1 WO 1991000327A1 US 9003700 W US9003700 W US 9003700W WO 9100327 A1 WO9100327 A1 WO 9100327A1
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Prior art keywords
boric acid
composition according
wood
solution
amount
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PCT/US1990/003700
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English (en)
Inventor
William J. Oberley
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Oberley William J
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Publication of WO1991000327A1 publication Critical patent/WO1991000327A1/fr

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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
    • C09K21/10—Organic materials containing nitrogen
    • 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
    • C09K21/02—Inorganic materials
    • 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
    • C09K21/02—Inorganic materials
    • C09K21/04—Inorganic materials containing phosphorus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K2240/00—Purpose of the treatment
    • B27K2240/30—Fireproofing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/16—Inorganic impregnating agents
    • B27K3/163—Compounds of boron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/52—Impregnating agents containing mixtures of inorganic and organic compounds

Definitions

  • compositions have long been used in treatment of wood and other cellulosic materials to provide a degree of fire retardant properties to such materials. Such properties most commonly have been obtained (1) by depositing on the surface of an article (either an article of manufacture or cellulosic particles from which a manufactured article is to be formed) a coating comprising either (a) a composition containing a finely divided solid material having fire retardant properties, or (b) an intumescent composition which, on exposure to the high temperatures of burning, decomposes pyrolytically to form a protective, insulating char layer on the coated article, or (2) by impregnating such materials with a fluid composition capable of penetrating the interstices of solid wood or other cellulosic material to be treated and which composition, and/or one or more decomposition products thereof which, on exposure to wood pyrolysis temperatures, reacts with wood before pyrolysis to form, primarily, carbon and water (in the form of steam) .
  • Typical of surface coating type composition are those comprising fire retardant solid materials in precipitated or otherwise finely divided form, such as: silica; carbonates and bicarbonates of sodium, potassium or ammonium; diammonium phosphate, or particulate metallic elements such as aluminum (Stossel U.S. Patent No. 4,076,540 which also provides an extensive description of prior art fire retardants) .
  • fire retardant solid materials such as: silica; carbonates and bicarbonates of sodium, potassium or ammonium; diammonium phosphate, or particulate metallic elements such as aluminum (Stossel U.S. Patent No. 4,076,540 which also provides an extensive description of prior art fire retardants) .
  • Such materials may be applied, in the form of solid powders, or pastes or suspensions to the surfaces of wood articles to be treated, for example as shown in Handa et al. U.S. Patent No. 3,811,992.
  • compositions suitable for the limited purpose of surface treatment of fibrous cellulosic materials or of wood particles for the manufacture of fiberboard and similar materials also include ionic complexes of nitrogen, phosphorus, oxygen and aluminum together with a boric acid compound and urea (Stossel U.S. Patent 4,076,540); and suspensions of boric acid with water-soluble borate salts such as those of ammonia, alkali metals and alkaline earth metals, for example borax (sodium tetraborate, Na 2 B 4 0 7 . 10 H 2 0) (Dietrich et al. U.S. Patent No. 4,801,404). Also in this category of fire retardant compositions is Schaar et al. U. S. Patent No.
  • 3,955,987 which is directed to a temporary intumescent coating in either dry powder form or in the form of an aqueous suspension containing monoammonium phosphate and/or diammonium phosphate as a fireproofing agent, urea and/or dicyandiamide (cyanoguanidine) as a gas forming agent to promote intumescence, a polyol such as mono-, di- or tripentaerythritol, starch, or sugars such as inositol, dextrose or sucrose as promoters of initial, low temperature intumescence, and titanium dioxide as a heat-reflecting agent.
  • a temporary intumescent coating in either dry powder form or in the form of an aqueous suspension containing monoammonium phosphate and/or diammonium phosphate as a fireproofing agent, urea and/or dicyandiamide (cyanoguanidine) as a gas forming agent to promote intumescence, a poly
  • Surface coating fire retardants may be in the form of a resin and also may contain a boron compound.
  • Such compositions include, for example, those containing a phosphoric acid-dicyandiamide-formaldehyde resin, such as disclosed in Surdyk U. S. Patent No. 3,874,990, wherein the resin component is used together with an alkaline borate such as a mixture of borax and boric acid (or sodium polyborate) and a binding resin such as a urea- or melamine-formaldehyde resin.
  • alkaline borate such as a mixture of borax and boric acid (or sodium polyborate)
  • a binding resin such as a urea- or melamine-formaldehyde resin.
  • boric acid ester resins impregnated into particle board and then hydrolyzed to deposit boric acid or boron oxide within the wood product (Short et al. U. S. Patent No.
  • Patent No. 4,076,540 polymers such as melamine, dicyandiamide, anhydrous borax, borax decahydrate (or boric acid) , ammonium polyphosphate and monoammonium phosphate — for addition to a plastic material during manufacture thereof (Schmittmann et al. U. S. Patent No. 4,438,028); Junega U. S. Patent No. 3,832,316 and Junega Canadian Patent No. 917,334, directed to fire retardants containingdicyandiamide, melamine, formaldehyde and phosphoric acid wherein a minor portion of the phosphoric acid may be substituted with another acid, such as boric acid; and Handa et al. U. S. Patent No.
  • 3,811,992 which discloses pretreating plywood with a silicate material such as sodium silicate or alkoxysilanol polymers with a deliquescent material such as ammonium bromide (which inhibits the low temperature flashing tendency of the silicon compounds) , then coating the pretreated plywood with a fire retardant in the form of an aqueous paste comprising 20-35% of a urea compound such as thiourea, dimethyl thiourea or monomethlyolmelamine, and 10-20 % of an ammonium halide with optional amounts of an organo- phosphorus or organo sulfur compound generating a fire retarding vapor at a pyrolysis temperature over about 400 deg.
  • a silicate material such as sodium silicate or alkoxysilanol polymers with a deliquescent material such as ammonium bromide (which inhibits the low temperature flashing tendency of the silicon compounds)
  • a fire retardant in the form of an aqueous paste comprising 20-35%
  • C for example tricresyl phosphate, glycerine phosphate, guanidine phosphate or ammonium sulfamate, a metal halide such as zinc chloride, a sulfate such as ammonium sulfate, and a weak acid such as boric acid or a weak acid compound such as ammonium borate or ammonium phosphate, an antimony compound such as antimony trioxide or antimony trichloride, a sulfoxide and formaldehyde.
  • a metal halide such as zinc chloride
  • a sulfate such as ammonium sulfate
  • a weak acid such as boric acid or a weak acid compound such as ammonium borate or ammonium phosphate
  • an antimony compound such as antimony trioxide or antimony trichloride
  • formaldehyde for example tricresyl phosphate, glycerine phosphate, guanidine phosphate
  • resinous and paste-like materials When used as surface coatings, resinous and paste-like materials, alone or together with other composition components, serve the fire retardant function by forming, on the surface of the treated wood article or wood particles from which an article is to be formed, an insulating carbonized coating, which, in some cases, may be foamed to increase the insulation properties.
  • an insulating carbonized coating which, in some cases, may be foamed to increase the insulation properties.
  • 3,811,992 shows the need for a 15 hour period for permeating a 4 mm thick wood panel at ambient temperature, followed by an elevated temperature treatment in an electric drier.
  • the above-described Short et al. U. S. Patent No. 4,076,871 discloses, as a necessary step for treating 1/4 inch thick hardboard panels, kiln heating panels coated with the borate-containing resin for 1-1/2 to 2 hours at 150°C to 165°C (302°F to 329°F) in order to cause the resin to penetrate into the board.
  • Prior art fire retardants suitable for impregnation of solid wood articles include, for example: Goldstein U. S. Patent No. 2,917,408 directed to a composition containing dicyandiamide and phosphoric acid; Goldstein U. S. Patent No. 3,159,503 wherein such a composition additionally contains a small amount of formaldehyde, and Steez U. S. Patent No. 4,174,223 which discloses a water-soluble composition comprising ammonium nitrate, ammonium polyphosphate, urea (over 30 weight percent) and, optionally, a base such as sodium hydroxide, and molasses, sugar or starch to aid in the retardation of flaming and afterglow.
  • Goldstein U. S. Patent No. 2,917,408 directed to a composition containing dicyandiamide and phosphoric acid
  • Goldstein U. S. Patent No. 3,159,503 wherein such a composition additionally contains a small amount of formaldehyde
  • Such compositions which also contain boron are exemplified by: Lewchalermwong U. S. Patent No. 4,725,382 wherein the fire retardant composition contains boric acid (in the form of the anhydrides, B 2 o 3 » , phosphorus pentoxide and ammonia; and Goettsche et al. U. S. Patent No. 4,461,721 which provides a wood preservative (and flame-proofing) composition containing a boric acid salt of a water-soluble amine such as monoethanola ine, water and sodium polyborate (or a mixture of boric acid and borax) .
  • boric acid salt of a water-soluble amine such as monoethanola ine, water and sodium polyborate (or a mixture of boric acid and borax
  • fire retardant compositions In addition to fire retardant action per se, fire retardant compositions must possess other important properties for their general acceptability and application. For example, acceptable fire retardants must not release or promote production of dangerous amounts of poisonous gases or fumes on burning.
  • acceptable fire retardants must not release or promote production of dangerous amounts of poisonous gases or fumes on burning.
  • many prior art fire retardants especially those having a resin as the effective ingredient, contain formaldehyde or other material forming formaldehyde as a high temperature reaction product.
  • Formaldehyde is considered a carcinogen, and products containing or releasing substantial amounts of formaldehyde during processing or on exposure to high, pre-pyrolysis temperatures pose significant health hazards.
  • Compositions comprising, as the effective fire retardant, compounds having a high degree of ambient temperature solubility in water are quickly leached out of impregnated wood products on exposure to weathering conditions, so are not suitable for treating wood articles intended for prolonged exterior and underground construction applications.
  • water-soluble materials which have been used in fire retardant compositions include phosphoric acid, ammonium salts such as ammonium phosphates, ammonium chloride or ammonium sulfate, and soluble metal salts such as chlorides of zinc, sodium or magnesium.
  • Patent No. 4,438,028 borax; Gottsche et al. U.S. Patent No. 4,461,721 — sodium tetraborate; Dietrich U.S. Patent No. 4,801,404 — alkali metal and alkaline earth metal salts) .
  • Metal-containing compositions especially those containing alkali metals and alkaline earth metals (e.g. as disclosed in the Dietrich patent and in Surdyk U.S. Patent No. 3,874,990), are glowing accelerators, that is, they promote wood combustion by glowing, and accordingly, compositions containing substantial amounts of such materials are undesirable components of fire retardant compositions. Such fire retardant materials have the further objectionable features of causing smoky burning and possible production of toxic fumes.
  • fire retardant compositions should be essentially non-hygroscopic or of low hygroscopicity, in order to avoid undue moisture absorption by treated wood products.
  • Oberley U. S. Patent No. 4,373,010 teaches that use of hygroscopic materials as fire retardants or as components of such compositions should be avoided to prevent blooming of the wood. Blooming results from water absorption by wood to an extent to form liquids allowing salts to migrate to and deposit salt crystals on the wood surface. This interferes with or prevents painting or other surface treatment of the wood product.
  • High water content of treated products containing water-soluble acids or acid-forming compounds also provides the conditions for corrosive attack of metals in contact with such products and, as discussed in more detail below, for acid hydrolysis of the wood cellulose.
  • Hygroscopic materials may be present as original components of the fire retardant or they may be formed as reaction products during preparation of the fire retardant composition, for example, on heating of the composition to solubilize the fire retardant component, or during drying of the treated wood products at elevated temperatures.
  • Fire retardant compositions comprising or containing substantial amounts of such hygroscopic materials are not generally useful and are to be avoided in many or most permanent wood-treating applications.
  • Hygroscopic materials which have been used in fire retardants prominently include, for example: urea — which is very hygroscopic (for example, the Oberley U.S. Patent No. 4,373,010 mentions that urea should be held under about 15% in order to avoid its strong hygroscopic action) ; alkali metal salts such as sodium chloride, sodium sulfate; other metal salts such as magnesium chloride, and ammonium sulfamate.
  • Examples of prior art fire retardant compositions comprising such hygroscopic materials include those described in: Handa et al. U. s. Patent No.
  • phosphoric acid and its salts are very common constituents of prior art fire retardants.
  • the term "phosphoric acid” refers to orthophosphoric acid, H 3 P0 4 and corresponding hydrated compounds such as 2H 3 P0 4 .H 2 0, which is the oxy acid of phosphorus most commonly available and used, and to which reference usually is made when such term is used; although the term phosphoric acid also may be used to include any or all of the other oxy acids of phosphorus such as: H 3 P0 3 (phosphorous acid) ; H 4 P 2 0 7 (pyrophosphoric acid) ; H 4 P 2 0 5 (pyrophosphorous acid) ; H ⁇ 1 ⁇ (hypophosphoric acid) , H 4 P 2 O g and HP0 3 (metaphosph ⁇ ric acids) , the polyphosphoric acids and mixtures of the above.
  • Orthophosphoric acid, H 3 P0 4 is a tribasic acid, having a pK, of about 2 in aqueous solution; accordingly, it is a strong acid.
  • pK refers to the negative logarithm of the dissociation constant, K, of a particular chemical compound to which reference is made.
  • pK, and pK ⁇ conveniently are used, respectively, as measures of acid or base strength. Acid of base strength decreases as pK A or pK ⁇ increases.
  • a strong acid such as phosphoric acid
  • phosphoric acid is a desirable ingredient of fire retardant compositions in order to react with wood at or below pyrolysis temperatures to form reaction products such as water, ammonia and non-combustible carbon — rather than combustible carbon containing tar and gases which result in heat generation and flame spread.
  • reaction products such as water, ammonia and non-combustible carbon — rather than combustible carbon containing tar and gases which result in heat generation and flame spread.
  • phosphoric acid per se is not a good fire retardant because it forms pyrophosphates at combustion temperatures and such compounds have no significant fire retardant action in accordance with usual test standards.
  • use of the highly acidic phosphoric acid per se would pose a manufacturing and handling safety hazard.
  • alkali metal phosphates and alkaline earth metal phosphates are not effective fire retardants because (in addition to the above-described afterglow effect which they promote) they retain a substantially neutral pH on heating and cannot serve as catalytic dehydrating agents to form carbon and water — a common theory of this mode of fire retardancy.
  • ammonium phosphates are acidic and have good fire retardance properties. Polyphosphates, of high acidity and good fire retardance, are formed under the high energy conditions prevailing at combustion temperatures. However, these desir ⁇ ible properties tend to be lost and the less fire retardant pyrophosphates tend to be formed under these conditions.
  • Ammonium phosphates release ammonia which reduces the rate of formation of the non-fire retardant pyrophosphates and thereby increases the time during which the desirable fire retardance properties of polyphosphates can be exerted.
  • a material such as phosphoric acid, which, under ambient conditions, exhibits high acidity, unfortunately has still other accompanying serious disadvantages.
  • fire-retardant compositions of high acidity and hygroscopicity are corrosive to metals in contact with the treated wood products. In general, the more acidic the fire retardant composition, the greater is the corrosion problem.
  • Acidic anions used in fire retardant compositions generally are selected from the following group: halide, e.g. bromide or chloride; sulfate; nitrate; phosphate, and borate - - in descending order of acidity.
  • Strongly acidic and hygroscopic compositions have the further disadvantage of seriously affecting the strength properties of wood products due to acid hydrolysis of the wood cellulose in prolonged contact with such fire retardant compositions. This effect only recently has been recognized and treated as a serious problem by regulatory agencies, the construction industry, and the insurance business. As a result, the use of fire retardant compositions causing dangerous strength loss due to their strongly acidic nature has been restricted or banned in several states.
  • Examples of highly acidic prior art fire retardant compositions include those disclosed in Handa et al. U.S. Patent No. 3,811,992; Schaar U.S. Patent No. 3,955,987; Stossel U.S. Patent No. 4,076,540, and Steez U.S. Patent No. 4,174,223.
  • DRICON aqueous solutions of fire retardant compositions with which solid wood is easily impregnated and containing, by weight of the composition prior to reaction, from 60 to 90% (preferably about 70%) of dicyandiamide plus phosphoric acid — which are reacted to form guanylurea phosphate (“GUP") — and from 10 to 40% (preferably about 30%) of boric acid.
  • GUP guanylurea phosphate
  • This combination of ingredients acts synergistically, the reaction product, "DPB,” exhibiting a greater reduction of fire weight loss as compared to the individual components of the mixture.
  • DPB reaction product
  • Such compositions are believed to be the only commercially produced fire retardant products for pressure treating of wood which currently are allowed unrestricted marketing in all states of the United States.
  • boric acid Due to the very low acidity of boric acid, its use in a fire retardant composition would be preferable to stronger acids such as phosphoric acid, especially under hygroscopic conditions, in order to reduce metal contact corrosion and the wood-degrading effects of acid hydrolysis.
  • acids such as phosphoric acid
  • boric acid alone has little fire retardant effect over a wide range of boric acid impregnant, for example, over a range from 0.5% to 2.5% boron retained in wood, for example as resulting from treatment under atmospheric pressure with an aqueous solution containing 10% by weight of boric acid.
  • boric acid as the sole or major component of fire retardant compositions, for example, in place of phosphoric acid, would be considered ineffective due to its low acidity and fire retardancy, as well as its limited low temperature solubility — even as those properties are enhanced by the phosphorus-based compositions of Oberley U.S. Patent No. 4,373,010.
  • the objects of this invention include the provision of improved boric acid fire retardant compositions, methods for making the same, and wood and other cellulosic products treated with such compositions.
  • a major portion of the solute phase comprises boric acid and a minor portion comprises materials increasing the water solubility of boric acid and its fire retardancy.
  • Such compositions are essentially free of or contain only controlled, low amounts of strong mineral acids or acid salts, are substantially non-hygroscopic or of controlled, low hygroscopicity.
  • Solid wood and other cellulosic products impregnated with such compositions are essentially non-corrosive to juxtaposed metals and the strength properties of the impregnated products are substantially unaffected by acid hydrolysis.
  • compositions for treating wood and other cellulosic products for example, but without limitation thereto, paper, cardboard, cotton, jute and hemp — (such cellulosic products generally being referred to herein as wood or wood products) , and comprising an aqueous solution, produced at ambient or only slightly elevated temperatures, in which the solute (that is, the charged materials, excluding water) contains boric acid in amounts upwardly of 40%, preferably at least 45%, and especially at least 50%, by weight of the solute, together with minor proportions of boric acid solubilizers and certain water soluble, nitrogen-containing synergists which enhance effectiveness as a fire retardant.
  • such compositions also have low metal corrosivity and are without significant hydrolytic degradation of the treated wood products.
  • boric acid commonly is used in reference to one or another of several compounds which differ from one another by the amount of chemical water content of the compounds.
  • Representative compounds include B(OH) 3 (boric acid) , HB0 2 (metaboric acid) , H 2 B 4 0 7 (tetraboric acid) , B 2 0 3 (boric oxide or boric anhydride) and mixtures thereof, and it is to be understood that such compounds may be referred to herein as boric acid unless otherwise indicated in a particular context.
  • B(OH) 3 the compound most generally referred to by the term boric acid, is a very weak monobasic acid which tends to form polymeric structures in mixed solutions with borates.
  • boric acid solubility in cold water (20°C) is about 5 parts per 100, increasing to about 40 parts/100 at 100°C.
  • Boric oxide, B 2 0 3 is slightly less soluble (about 1.1 part per 100 in water solution at 0°C and about 16 parts/100 at 100°C) and, with water, forms B(0H) 3 .
  • the comparatively low ambient temperature water solubility of boric acid is of advantage in boric acid-based fire retardants in that wood treated with such compositions can be used for certain outdoor applications, such as temporary construction, while retaining fire retardancy longer than compositions containing more soluble ingredients as above described.
  • boric acid is the least acidic of the acid anions commonly found in fire retardant compositions, being of nearly neutral pH in aqueous solution at ambient temperatures.
  • the basic equilibrium constant, pK A , for boric acid, B(OH) 3 is in the range of about 7 to about 9 depending upon the particular structure and molar concentration in water solution.
  • boric acid is a very "weak” acid as compared, for example to phosphoric acid and the other "strong" mineral acids above-described as commonly used in prior art fire retardant compositions.
  • boric acid alone as a fire retardant is due to the formation of boron oxide, B 2 0 3 , which is non-fire retardant — but is a strong glow inhibitor.
  • B 2 0 3 boron oxide
  • a fire retardant composition based on ammonium phosphate is a good fire retardant because of the slow loss of ammonia, a combination of boric acid and ammonia is not.
  • elevated temperatures e.g. above about 250°C-300°C.
  • a superior fire retardant composition can be made by providing, in combination with boric acid and water, a material which substantially increases the low temperature water solubility of boric acid in aqueous solution, and a non-acidic nitrogen-containing material which is not subject to the above- described shortcomings of an ammonia-boric acid system and which, with boric acid, provides a synergistic effect in enhancing fire retardancy of wood products treated with such compositions.
  • Useful nitrogen-containing synergists include such water soluble, nitrogen-containing compounds as semicarbazide, guanidine, cyanamide, dicyandiamide, urea and guanylurea.
  • Melamine, biuret and oxamide also are useful synergists, but they have low water solubility at the comparatively low temperatures normally used for production of the compositions of this invention. If such materials are used as the sole synergist(s) , their solubility can be increased by use of an appropriate additional solubilizing agent. For example, solubilization of one ol of melamine can be obtained with use of about 1/2 mol of formaldehyde.
  • these synergist materials are not adequate solvents for boric acid, but in combination with boric acid they provide excellent improvement in fire retardancy as compared to such materials or boric acid alone.
  • a composition containing, dicyandiamide (“dicy”) as the synergist there may be considered, for example, a composition containing, dicyandiamide ("dicy") as the synergist.
  • the "dicy” hydrolyzes to guanylurea; the guanylurea reacts with boric acid to form the corresponding acidic borate; the borate is hydrolyzed to guanidine borate and ammonia; the guanidine borate is further hydrolyzed to urea-boric acid adduct and additional ammonia; the adduct further hydrolyzes to transient ammonium borate which ultimately leads to the formation of boron oxide.
  • Such systems therefore provide fire retardant compositions which are essentially non-acidic at room temperature — hence they do not result in acid hydrolysis of impregnated wood — but, on heating to wood combustion temperatures, they become strongly acidic and hence are good fire retardants.
  • Effective solubilizing agents for the boric acid include strongly basic non-alkali metal, non-alkaline earth metal nitrogen-containing compounds, for example, those having a pK value under about 5, preferably under 4, (the PK ⁇ value for ammonia in aqueous solution at 25°C is 4.75) such as: ammonia; basic amines, including primary, secondary and tertiary alkylamines and alkanolamines (amino alcohols) such as mono, di- and triethylamines; mono-, di- and tripropylamines; mono-, di- and triethanolamines, and mono-, di- and tripropano- lamines, and addition compounds such as hexamethylenetetramine and those formed by reaction of formaldehyde (for example, when used as a solubilizer for certain synergists, as aforesaid) and amines such as urea or melamine, or dicyandiamide used as synergists
  • Suitable boric acid solubilizers also include substantially pH-neutral or weakly basic nitrogen-containing compounds (pK of about 5 or greater) , for example: hydrazine; hydroxylamine, ammonium carbonates and ammonium carbamate.
  • Another type of suitable solubilizer includes alcohols such as the lower (water soluble) saturated monohydric alcohols such as methanol, ethanol, n-propanol, isopropanol, and butyl and amyl alcohols; and polyols, including dihydric alcohols such as ethylene glycol and propylene glycol, trihydric alcohols such as glycerol (glycerine), higher polyhydric alcohols, for example, mannitol and sorbitol, and the monosaccharides and disaccharides.
  • pK substantially pH-neutral or weakly basic nitrogen-containing compounds
  • Preferred monohydric alcohols are methanol and ethanol, especially methanol.
  • glycerol is preferred.
  • sucrose is preferred.
  • sugars are readily impregnated into wood products, when the products are dried, they tend to have a somewhat sticky surface. Therefore such solubilizers are not preferred for some applications.
  • Solubilization of boric acid is promoted by its reaction with the lower alcohols and polyhydroxy compounds such as the trihydric alcohol, glycerol, and the monosaccharides and disaccharides, alone or mixed with ammonia, to form equilibrium borate esters and complexes which effectively increase the rate and extent of solution of boric acid.
  • the lower alcohols and polyhydroxy compounds such as the trihydric alcohol, glycerol, and the monosaccharides and disaccharides, alone or mixed with ammonia
  • solubilizers which can react to form resinous materials
  • resinous materials for example borate esters or formaldehyde reaction products
  • solubilizers required for effective boric acid solubilization are limited to an amount sufficiently small as to avoid the formation of such quantities of viscous resinous materials as would interfere with the impregnation of wood products or give rise to the need for high temperature curing of the treated products.
  • the compounds formed as reaction products of boric acid with the contemplated boric acid solubilizers do not completely volatilize or precipitate under ambient conditions. After drying of wood products impregnated with such compositions, some of these reaction products remain in the wood.
  • Some of the contemplated nitrogen-containing solubilizers for example, the alkylamines, also may serve a synergistic function in the compositions of this invention. Such action depends upon the particular organic radical and the nature of the chemical bond involved. Depending upon such factors, as well as the decomposition rate and the combustible carbon content of such materials, such materials may tend to promote flame spreading upon exposure to burning temperatures. In general, the larger the organic radical, the more fuel it adds and the more combustible it is. However, the latter characteristic is not contraindicative of use of such materials in my fire retardant compositions, where, for example, the amount required for solubilization is relatively small and the synergistic effect is pronounced. In such cases, the advantages gained in boric acid solubilization and synergistic effect on fire retardance may outweigh the flame spreading potential of such materials.
  • Mono- and diammonium phosphates and guanylurea phosphate also are useful as boric acid solubilizers, and these materials also have the desirable characteristic of acting, with boric acid, as synergists in effect on fire retardancy.
  • Phosphoric acid in limited amounts, also can serve a role as a supplemental fire retardant in the compositions of the invention.
  • such materials are limited in combined amount to less than about 20%, preferably less than 15 or 16% by weight of the solute (charge materials, excluding water) .
  • the boric acid content can be reduced by an amount about equal to the phosphoric acid equivalent in the phosphorus compound.
  • the compositions of the invention are most effective when the molar ratio of N to B or B+P is from about 0.5:1 to about 2:1, preferably about 0.8:1 to 1.5:1, depending on the degree of synergis of the nitrogen-containing synergist compound.
  • compositions of the invention can be prepared in the form of a dry powder mixture of those components which are of solid form at ambient temperatures. If ammonia is included in the composition, the dry formulation may include ammonium carbonate. Other components, in liquid form at ambient temperature, may be added when forming an aqueous fire retardant solution.
  • Aqueous solutions containing the contemplated solubilizers and combined solubilizer/synergists, can be prepared at fairly low temperatures and containing larger amounts of boric acid than heretofore have been employed. Thus, it is possible to prepare such solutions containing boric acid in amounts upwardly of 5% to about 15 or 20% by weight of the solution and wherein the boric acid comprises over 40 to 45% to about 70% by weight of the charge materials.
  • solutions for use directly in treating most wood products may contain boric acid in amount from about 5 to about 9 or 10 weight percent of the solution and wherein the boric acid comprises, by weight percent of the charge materials, from about 45%, especially at least 50%, to about 65%, and particularly about 60%.
  • Preparation of aqueous solutions of the contemplated fire retardant compositions can be carried out by adding the component chemicals to water at a temperature from close to 0°C, especially about 20°C. , to about 100°C.
  • solution of boric acid may require use of solubilizers of greater solubilization capacity and/or in greater amounts than required at higher temperatures.
  • the higher end of such range is not necessary and is not preferred in preparation of compositions containing materials, such as ammonia, having high rates of volatilization at such elevated temperatures.
  • a preferred method is to add the boric acid and solubilizer(s) to water and agitate the mixture until the boric acid is dissolved, and then add the synergist(s) followed by any remaining water and other ingredients, and then allowing the solution to cool to ambient temperature.
  • all of the chemicals can be added, for example, to about 20°C to 45°C water, and agitated until the chemicals are dissolved.
  • Such aqueous solutions may be prepared with solute contents suitable for use directly as wood treating compositions, or they may be prepared in the form of more concentrated solutions which may be diluted with further amounts of water, as desired.
  • the factor ultimately determining the amount of solubilizer to be used in making a fire retardant treating solution in accordance with this invention is the amount of boric acid (and synergist) to be introduced into a particular wood product to be treated. This depends upon the degree of fire retardance desired for the wood product and the solution absorption capability of the wood product at a particular treating temperature. Once such factors are known, the required amount of solubilizer can be determined in terms of the corresponding required concentration of boric acid in the treating solution and, in turn, the solubilization capacity of a particular selected solubilizer and the temperature to be used in making the fire retardant treating solution.
  • Factors affecting solubilization capacity include, for example, its basicity and rate and extent of reaction with boric acid and with other ingredients of the composition, for example by formation of addition compounds, borate esters or complexes, or the ability to increase the acid strength and availability of boric acid for reaction.
  • Other known chemical and physical characteristics of the solubilizer such as volatility, ignition temperature, and flame spreading or inhibiting tendency, also are to be considered in selecting and determining the amount of particular solubilizers.
  • a practical advantage of the preferred, solubilizer- containing compositions of this invention and the method of preparing aqueous solutions of those compositions is that the solutions can be made at the above-described preferred, comparatively low temperatures in the range of about 20°C. or 30°C. to about 45°C. Such processing requires less energy than do temperatures in the higher portion of the broad temperature range, and at the lower temperatures there is less loss of any volatile process materials. Moreover, such solutions can be stored and handled at ambient temperatures without precipitation of solute components. Storage of aqueous solutions of the compositions of the invention normally is at temperatures well above freezing, in order to avoid precipitation of dissolved compounds. However, these compositions have the further advantage that, if frozen, they can be reheated and the solute redissolved without reducing the effective fire retardancy of the compositions. Nevertheless, such additional steps are costly and normally should be avoided.
  • the amount of solubilizers required in preparing compositions in the lower portions of the processing temperature range may be as little as about 8% to about 30%, and preferably from about 10% to about 20% by weight of the charge materials.
  • compositions having relatively low boric acid contents in the aqueous treating solutions can be made by carrying out the process at temperatures upwardly of about 50°C, without the use of boric acid solubilizers.
  • solubilizer also can be omitted under certain, limited conditions, for example where high boric acid concentrations are not needed, or where limited absorption capacity of a particular wood product precludes impregnation of large amounts of fire retardant, or where the corresponding boric acid concentration of the treating solution is sufficiently low to avoid precipitation under ambient storage and handling temperatures, or where the practical and economic effects of either reheating to resolubilize precipitated solute, or of storing and handling of the solution at elevated temperatures to prevent precipitation may be feasible.
  • the quantity of synergist(s) will depend upon the degree of fire retardancy required and the particular synergist(s) , or combined solubilizer/synergist(s) which are selected.
  • the required amount of such materials generally may range from about 25 to about 40%, preferably from 30 to 38% by weight of the (non-aqueous) charge materials, except that urea is restricted in maximum amount to about 15 to 17% in order to limit undesirable hygroscopicity of the compositions. Amounts of urea up to such maximum limit are useful, not only to aid in solubilization of boric acid, but also (by virtue of its strong hygroscopicity) to serve to keep treated wood products from completely drying out by retaining a small amount of water in the products.
  • the fire retardant composition contains a component which acts both as a solubilizer and as a synergist
  • a component which acts both as a solubilizer and as a synergist such multiple functions must be considered in determining the total amounts of such components and other solubilizers and synergists required to obtain a desired degree of fire retardancy.
  • the total amount of such materials together with non-solubilizing synergist(s) may range, for example, from about 15% to about 35%, and preferably from about 20% to about 30% of the weight of the charge materials.
  • water, boric acid, dicyandiamide (synergist) and urea serving as a combined solubilizer and controlled water retention agent
  • urea serving as a combined solubilizer and controlled water retention agent
  • Boric acid is an effective biocide.
  • additional biocides and other materials may be added to the compositions of the invention, but such additives should not materially affect the non-resinous, non-hygroscopic and low acidity nature of the compositions or their fire retardant properties, and should not contribute other undesirable characteristics, such as production of noxious fumes, afterglow, etc. on high temperature exposure of the treated wood products.
  • Aqueous solutions of the fire retardant compositions of this invention can be used to treat wood products by any one of the various techniques which are well known in the art. Examples of such methods include dipping, soaking and vacuum or vacuum-pressure impregnation. The particular technique used will be determined by such factors as the species of wood being treated, the thickness of the wood product, the degree of fire retardancy required and the intended end use of the treated wood product. The treating method and conditions to be employed also are factors to be considered in determining the solute composition and component concentrations of the aqueous treating solution.
  • a wood product After treatment of a wood product, it thereafter may be dried in a conventional manner at ambient temperature. Alternatively, drying may be accelerated by heating the product, for example, in a kiln to a temperature of from about 40°C to about 65°C, for a time sufficient to reduce the wood moisture content to about 10 to 20 percent, normally around 10%. Because the fire retardant compositions of the invention are essentially non-resinous, an extended, high temperature (e.g. 65°C or greater) curing cycle is not required. Therefore, wood strength is not impaired.
  • an extended, high temperature e.g. 65°C or greater
  • a 12.5% aqueous treating solution is prepared from 61.84 gm. (1 mole) boric acid, 11.22 g . (0.18 mole) monoethanolamine, 11.22 gm. ammonium hydroxide (3.25 gm. - 0.19 mole NH 3 ) , 18.02 gm. (0.30 mole) urea, 6.15 gm. (0.08 mole) dicyandiamide, and 669.39 gm. (37.1 moles) water.
  • Half of the water is heated to 45°C and, while agitating, the boric acid, urea and dicyandiamide are added.
  • the boric acid, urea and dicyandiamide are added.
  • the ethanolamine and ammonium hydroxide are added and agitation is continued until all of the components are in solution. The remainder of the water is added and the solution is cooled to room temperature.
  • Example 1 A composition in accordance with Example 1 was prepared in sufficient amount to accommodate the immersion therein and impregnation therewith of four ponderosa pine fire tube specimens having dimensions of 3/8 inch x 3/4 inch x 40 inches. The specimens were submersed in a treating cylinder designed for pressure impregnation and a vacuum of about 30 inches of Hg was applied for 30 minutes, followed by a pressure impregnation period of 3 hours at about 150 psi. The pressure then was released and the specimens removed from the cylinder and allowed to air dry for one day and then oven dried at about 50°C until an equilibrium moisture content of about 5 to 10% was reached.
  • Other compositions, identified as Examples 2, 3 and 4 in Table 1 below, were similarly prepared and used to similarly treat additional similar wood samples. The ammonia in the formulations of Examples 1-3 is volatile and is removed essentially completely from the wood during drying.
  • the thus-treated specimens as well as similar untreated wood control samples, and similar samples treated only with boric acid, monoethanolamine or urea, were subjected to fire tube tests in accordance with the procedure of ASTM E69-50. According to this standard, fire tube weight loss under 30% is considered acceptable fire retardancy.
  • the specimens were oven-dried and equilibrated to a moisture content of about 5% and placed in a metallic tube having vent holes. The bottom ends of the specimens were positioned a distance of one inch from the top of a burner and a calibrated flame then was applied to the bottom of the samples. The burner was adjusted to provide a flame height of 11 inches and a temperature at the top of the fire tube (in the absence of a sample) of 175°C to 180°C.
  • DRICON is a trademark of Hickson, Ltd.
  • jGUP guanylurea phosphate
  • HMTA hexamethy1enetetramine
  • Example 1 the fire retardancy of the wood treated with the phosphorus-free Example 1 composition is about equal to that of the sample treated with the high phosphorus, relatively highly acidic (about pH 3.5) DRICON composition.
  • compositions such as that used in Example 1 have the further advantage over acidic phosphorus-containing compositions such as that of Example E, of being nearly neutral (pH is in the range of about 6.5 to about 6.9) and hence free of harmful wood degradation by acid hydrolysis.
  • Examples 2 and 3 of Table 1 further illustrate the compositions of the invention. These compositions contain high percentages (respectively 58.1% and 50%) of boric acid together with other boric acid solubilizers (ammonia and hexamethylenetetramine) and supplemental solubilizers/ synergists (phosphoric acid in Example 2 and guanylurea phosphate in Example 3 — both of which compounds are limited to 15% or less in order to avoid high acidity of the compositions) . Both Examples 2 and 3 show excellent fire retardancy. As in the case of Example 1, fire tube weight loss is in the range of 20 - 27%, as compared to a weight loss of 85% for untreated wood (Example A) and 65-70% for boric acid alone.
  • boric acid solubilizers ammonia and hexamethylenetetramine
  • supplemental solubilizers/ synergists phosphoric acid in Example 2 and guanylurea phosphate in Example 3 — both of which compounds are limited
  • the amount of the monoethanolamine solubilizer is determined as a function of the minimum amount at which, in the presence of the synergists, urea and dicyandiamide, the desired amount of boric acid can be dissolved in water at the predetermined, practically low temperature, without the addition of so much monoethanolamine that unacceptable flame spreading would occur upon exposure to wood combustion temperatures.
  • the amount of monoethanolamine required for such purpose can be reduced, and its contribution to flame spreading decreased, by using, in conjunction with the amine, a second solubilizer, such as ammonium hydroxide, which adds no fuel value to the composition.
  • the amount of fire retardant material needed to achieve acceptable fire retardancy is dependent upon factors such as wood species and density, and conditions of manufacturing a wood article, such as plywood. For example, such retention using an efficient fire retardant varies from as little as 2.5-3.0 pounds per cubic foot for Douglas fir lumber to retentions as high as 6 pounds per cubic foot for Southern yellow pine plywood. For effective fire retardance, the amount of effective fire retardant should be slightly greater than the threshold level determined to provide such adequate fire retardancy. Thus, from Examples 2-3 of Table 1, it will be seen that, with use of the compositions of this invention, adequate fire retardancy (below 30% fire tube weight loss) is achieved at retentions less than 6 pounds per cubic foot of the ponderosa pine samples.
  • Example E As also shown in Table 2, the best and nearest comparable prior art fire retardant composition (“DRICON") , Example E, has a B:P weight ratio less than 0.5:1, whereas the compositions of the invention as shown in Table 1 have a B:P weight ratio over 3:1, i.e. over 6 times greater. Similarly, on the basis of weight percent of retained fire retardant, in terms of equivalent boric acid and phosphoric acid, the boric acid/phosphoric acid ratio, for the phosphoric acid-containing Examples 2 and 3, is about 7-8 times greater than that for Example E.
  • Example 4 of Table 1 contains borax as well as boric acid.
  • an acceptable level of retained fire retardant for example, 5.7 pounds per cubic foot as shown for the second test composition of Example 4
  • the fire retardancy of such compositions is much less (58% fire tube weight loss) than the preferred compositions of this invention.
  • This latter test illustrates the disadvantage of the use of metal salts such as borax in fire retardant compositions due to the action of such salts in reducing their effectiveness by deactivating boric acid as a fire retardant, on a mol-for-mol basis.
  • a sodium-containing formulation such as that of Example 4 can provide reasonable fire retardancy and satisfactorily low hygroscopicity and acidity
  • fire retardancy equal to that of the preferred compositions of this invention is possible only if the amount of fire retardant is increased to a level at which the impregnated wood becomes unacceptably dense and brittle — as shown in the first of .the two test compositions of Example 4.
  • fire retardant performance of such compositions can be improved by increasing the amount of dicyandiamide and/or urea, higher than optimum retentions still are required.
  • compositions of this invention are substantially less costly than the "DRICON" compositions.

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Abstract

Compositions d'ignifuge ameliorés et méthodes de fabrication de telles compositions, ainsi que le bois et d'autres produits cellulosiques traités avec de telles compositions qui contiennent une quantité importante d'acide borique et une petite quantité (a) d'un ou plusieurs matériaux synergiques qui à l'aide de l'acide borique, augmentent les propriétés ignifuges des produits ainsi traités, en comparaison avec les produits traités à l'acide borique ou seulement avec le synergiste, et (b) facultativement un ou ou plusieurs agents de solubilisation qui accroissent la solubilté de l'eau de l'acide borique. Les compositions presentent un pH neutre et ne provoquent pas de corrosion métallique ou hydrolyse acide des produits traités.
PCT/US1990/003700 1989-06-28 1990-06-26 Ignifuges et produits les incorporant WO1991000327A1 (fr)

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WO2002070215A3 (fr) * 2001-03-01 2003-11-06 Arch Wood Protection Inc Produit ignifuge ameliore
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WO2012164143A2 (fr) 2011-05-30 2012-12-06 Fp Wood Oy Composition ignifugeante et procédé pour le traitement du bois
CN104371747A (zh) * 2014-09-30 2015-02-25 滁州斯迈特复合材料有限公司 空调机箱用阻燃剂
GB2521383A (en) * 2013-12-18 2015-06-24 Al Hajam Establishment Volume Trading Fire retardant composition
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WO2022243332A1 (fr) 2021-05-17 2022-11-24 Ecochem International Nv Composition ignifuge pour produits en fibres naturelles
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US5401497A (en) * 1991-03-22 1995-03-28 Goldwell Ag Composition for permanent waving of human hair and use of ammonium carbamate in such compositions
EP1069173A1 (fr) * 1999-07-05 2001-01-17 Manoochehr Shafaei Matériau non-inflammable
WO2002070215A3 (fr) * 2001-03-01 2003-11-06 Arch Wood Protection Inc Produit ignifuge ameliore
EA009912B1 (ru) * 2001-03-01 2008-04-28 Арч Вуд Протекшн, Инк. Улучшенный антипирен
WO2007109898A1 (fr) * 2006-03-28 2007-10-04 Hydro-Quebec Matiere solide a base de polysaccharides impregnee et a stabilite amelioree procedes de preparation et solutions d'impregnation utilisees
US8298582B2 (en) 2006-03-28 2012-10-30 Hydro-Quebec Polysaccharide-based impregnated solid material with improved stability, processes for the preparation thereof and impregnating solutions used
DE102007005527A1 (de) * 2007-02-03 2008-08-07 Alzchem Trostberg Gmbh Verfahren zur Behandlung von Holzteilen
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WO2012164143A2 (fr) 2011-05-30 2012-12-06 Fp Wood Oy Composition ignifugeante et procédé pour le traitement du bois
GB2521383A (en) * 2013-12-18 2015-06-24 Al Hajam Establishment Volume Trading Fire retardant composition
WO2015092410A1 (fr) * 2013-12-18 2015-06-25 Al-Hajam Establishment (Volume Trading) Composition de retardateur de flamme
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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
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
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
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