Fire retardant agent

Abstract

A fire retardant agent comprising calcium or magnesium mineral borates or calcium or magnesium meta borate and a halogen source; a method of rendering organic materials generally of a hydrocarbon nature, such as plastic and rubber polymers, cellulosics, resins and oils, etc., fire retardant by introducing into said organic materials calcium or magnesium mineral borates or calcium or magnesium meta borate and a halide; articles, laminates, coatings, foams, papers, fabrics, etc. containing calcium or magnesium mineral borates or calcium or magnesium meta borate and a halide of atomic weight greater than 19.

What is claimed is: 
     
       1. A fire retardant agent comprising a calcium .[.or magnesium.]. mineral borate or a calcium .[.or magnesium.]. metaborate and a halogen source, said halogen having an atomic weight greater than 19. 
     
     
       2. A composition according to claim 1 wherein the calcium .[.or magnesium.]. mineral borate is selected from the group consisting of 2CaO.B 2  O 3 .H 2  O; CaO.B 2  O 3 .6H 2  O; CaO.B 2  O 3 .4H 2  O; CaO.B 2  O 3 .3.65H 2  O; 2CaO.3B 2  O 3 .H 2  O; 2CaO.3B 2  O 3 .13H 2  O; 2CaO.3B 2  O 3 .9H 2  ; 2CaO.3B 2  O 3 .7H 2  O; CaO.B 2  O 3 .2H 2  O; Colemanite, .[.Boracite,.]. Sassolite, Ulexite, Tertschite, Probertite, Princeite, Pandermite, Inyoite, Meyerhofferite, Nobleite, Gowerite, Ginorite, Calciborite, .[.Inderborite, Hydroborocite,.]. K 2  O.CaO.4B 2  O 3 .12H 2  O; (NH 4 ) 2 .CaO.4B 2  O 3 .12H 3  O and Na 2  O.2CaO.5B 2  O 3 .16H 2  O.[.; Pinnoite, Ascherite, Szaibelyite, Inderite, Kurnakovite, Preobrazlienskite, M g  O.2B 2  O 3 .8.5H 2  O; MgO.3B 2  O 3 .7.5H 2  O; MgO.3B 2  O 3 .5H 2  O; Suanite, (NH 4 ) 2  O.MgO.3B 2  O 3 .15H 2  O and (NH 4 ) 2  O.MgO.3B 2  O 3 .7H 2  O.].. 
     
     
       3. A composition according to claim 2 wherein the calcium .[.or magnesium.]. borate preferably has a negligable solubility in water at 25° C. 
     
     
       4. A composition according to claim 2 wherein the halogen source is selected from the group consisting of halogen-containing polymers, halogen-containing rubbers, halogen-containing phenolics, halogenated aliphatic compounds and halogenated aromatic compounds. 
     
     
       5. A composition according to claim 4 wherein the halogen source is selected from the group consisting of halogenated acids where the halogen is on a non-carbonyl atom, said acid having between 3 and 24 carbon atoms and being saturated or unsaturated, polyethers, ketones where at least one substituent attached to the carbonyl has between 4 and 12 carbon atoms, aldehydes where the substituent attached to the carbonyl group has between 4 and 12 carbon atoms, anhydrides of halogenated acids where the halogen is on a non-carbonyl atom and the group attached to the carbonyl atom has between 3 and 24 carbon atoms, primary alcohols in which the group attached to the OH radical has between 4 and 12 carbon atoms, secondary alcohols in which at least one group attached to the carbon atom to which the OH radical is attached has between 4 and 12 carbon atoms, acid halides of C 2  to C 12  atoms, monosaccharides, polysaccharides, starch, cellulose, esters of said acids, thio derivatives of said acids, aldehydes, ketones and alcohols where the sulfur atom replaces the oxygen atom, aryl compounds of C 6  to C 18  carbon atoms, aryl ethers where the organic group attached to the oxygen contains at least 4 carbon atoms, aryl aldehydes where the organic radical attached to the oxygen atom contains between 4 and 12 carbon atoms, arylketones where at one organic group attached to the oxygen atom has between 4 and 12 carbon atoms, alkenyl aryl compounds where the alkenyl group contains between 4 and 12 carbon atoms, aryl alcohols where at least one organic radical attached to the carbon bearing the hydroxy group has between 4 and 12 carbon atoms, hydroxy aryl compounds, sulfonated aryl compounds, nitrated aryl compounds, aryl acid halides of C 2  to C 12  atoms in the acid halide group, cyano aryl compounds, mercapto aryl compounds, amine aryl compounds, aromatic dicarboxylicacids and their anhydrides, cyclic and heterocyclic organic chemicals having between 5 and 10 members in the ring. 
     
     
       6. A composition according to claim 2 wherein said halogen source is selected from the group consisting of a compound having the formula ##STR2## its acids, mixed acids, bi-acids, mixed esters, bi-esters and anhydrides, wherein R can be H, C 1  -C 12  alkyl or a halogenated derivative thereof, 1,2,3,4-tetrachloro-5,5-dimethoxycyclopentadiene, 1,2,3,4-tetrachlorocyclopentadiene, nonachlorobicyclo[3.2.0]heptene-2, 1,2-dichloro-3,3,4,4,5,5-hexafluorocyclopentene, decachloropentacyclo[5.3.0.0 2 ,6.0 4 ,10.0 5 ,9 ]decan-3-one, octachlorocyclopentene, bis(pentachloro-2,4-cyclopentadiene-1-yl), 1,2,3,3,5,5-hexachloro-4-(dichloromethylene)-cyclopentene, perchloropentacyclo[5.2.1.0 2 ,6.0 3 ,9.0 5 ,8 ]-decane, 2,3,4,4,5-pentachloro-2-cyclopentene-1-one, 1,2,4-trichlorcyclopentene-3,5-dione, 1,2,3,4,7-hexachlorobicyclo[2.2.1]-2,5-heptadiene, 1,4,5,6,7,7-hexachlorobicyclo[2.2.1]-5-heptene-2,3-dicarboxylic acid, 1,4,5,6,7,7-hexachloro-2,3-bis(chloromethyl)-bicyclo[2.2.1]-5-heptene, 1,4,5,6,7,7-hexachloro-2-(1,2-dichloroethyl)-bicyclo[2.2.1]-5-heptene, 1,4,5,6,7,7-hexachloro-2-carboxybicyclo[2.2.1]-5-heptene, 1,4,5,6,7,7-hexachloro-2,3-bis(hydroxymethyl)-bicyclo[2.2.1]-5-heptene, undecachloropentacyclo [5.3.0 2 ,6.0 4 ,10.0 5 ,9 ]-3-decyclorosulfonate, 4,5,6,7,8,8-hexachloro-3a, 7a-dihydro-4,7-methano-indene, 1,2,3,4,10,10-hexachloro-1,4,4a,5,8,8a-hexahydro-1,4,-endo, exo-5,8-dimethanonaphthalene, 1,4,5,6,7,7-hexachloro-2-formylbicyclo[2.2.1]-5-heptene, 1,4,5,6,7,7-hexachloro-2-cyanobicyclo[2.2.1]-5-heptene, and hexachlorocyclopentenones. 
     
     
       7. A composition according to claim 4 wherein the mineral is present together with the halogen such that the weight ratio of mineral borate to halogen is between 1 and 8. 
     
     
       8. A composition according to claim 7 wherein said ratio is between 1 and 4. 
     
     
       9. A composition comprising a normally flammable organic material and the fire-retardant composition of claim 2. 
     
     
       10. A flame-stabilized composition comprising a normally flammable organic material and the fire retardant composition of claim 5. 
     
     
       11. A flame-stabilized composition comprising a normally flammable organic material and the flame retardant composition of claim 6. 
     
     
       12. A flame-stabilized composition comprising a normally flammable organic material and the flame retardant composition of claim 6, the weight ratio of mineral to halogen source being between 1 and 8 and the mineral being present in the composition in an amount between 2 and 400 parts per part of organic material. 
     
     
       13. A flame-stabilized composition according to claim 12 wherein the amount of mineral introduced is between 5 and 50 parts per 100 parts of organic material and the weight ratio of mineral to halogen is between 1 and 4. 
     
     
       14. A flame stabilized composition according to claim 13 wherein the organic material is selected from the group consisting of polymers of alpha olefins, vinyl polymers, polyamides, polyacetals, polyurethanes, polyesters, rubbers and latexes. 
     
     
       15. A flame-stabilized composition according to claim 14 wherein said organic material is a polymer of an alpha olefin. 
     
     
       16. A flame stabilized composition according to claim 15 wherein said organic material is a polypropylene. 
     
     
       17. A flame-stabilized composition comprising a normally flammable organic material selected from the group consisting of polyethylene, polypropylene, polybutene-1, polyisobutylene, polyvinyl chloride, polymethylmethacrylate, polyethylmethacrylate, polyacrylonitrile, polyvinylalcohol, polyvinylacetate, polyvinylbutyral, polystyrene, nylon 6, nylon 6/6, natural and synthetic rubbers, natural and synthetic latexes, polystyrene-butadiene, polyacrylonitrile acrylic polyethylenes, chlorosulfonated polyethylenes, epichlorohydrin and its polymers, ethylene-propylene copolymers, ethylene-propylene-diene terpolymers, polyisoprene-acrylonitrile, polybutadiene, polychloroprenes, polyisoprenes, polystyrene-isoprene and polyurethane, said composition containing a flame retardant composition which comprises a calcium or magnesium mineral borate and a source of a halide of atomic weight greater than 19, said source of halide being selected from the group consisting of a compound having the formula ##STR3## its acids, mixed acids, bi-acids, mixed esters, bi-esters and anhydrides, wherein R can be H, C 1  -C 12  alkyl or a halogenated derivative thereof, 1,2,3,4-tetrachloro-5,5-dimethoxycyclopentadiene, 1,2,3,4-tetrachlorocyclopentadiene, nonachlorobicyclo[3.2.0]heptene-2, 1,2-dichloro-3,3,4,4,5,5-hexafluorocyclopentene, decachloropentacyclo[5.3.0.0 2 ,6.0 4 ,10.0 5 .9 ]decan-3-one, octachlorocyclopentene, bis(pentachloro-2,4-cyclopentadiene-1-yl), 1,2,3,3,5,5-hexachloro-4-(dichloromethylene)-cyclopentene, perchloropentacyclo[5.2.1.0 2 ,6.0 3 ,9.0 5 ,8 ]-decane, 2,3,4,4,5-pentachloro-2-cyclopentene-1-one, 1,2,4-trichlorocyclopentene-3,5-dione, 1,2,3,4,7-hexachlorobicyclo[2.2.1]-2.5-heptadiene, 1,4,5,6,7,7-hexachlorobicyclo[2.2.1]-5-heptene-2,3-dicarboxylic acid, 1,4,5,6,7,7-hexachloro-2,3-bis(chloromethyl]-bicyclo [2.2.1]-5-heptene, 1,4,5,6,7,7-hexachloro-2-(1,2-dichloroethyl)bicyclo [2.2.1]-5-heptene, 1,4,5,6,7,7-hexachloro-2-carboxybicyclo [2.2.1]-5-heptene, 1,4,5,6,7,7-hexachloro-2,3-bis(hydroxymethyl)-bicyclo[2.2.1]-5-heptene, undecachloropentacyclo[5.3.0 2 ,6.0 4 ,10.0 5 ,9 ]-3-decyclorosulfonate, 4,5,6,7,8,8-hexachloro-3a, 7a-dihydro-4,7-methano-indene, 1,2,3,4,10,10-hexachloro-1,4,4a,5,8,8a-hexahydro-1,4,-endo, exo-5,8-dimethanonaphthalene, 1,4,5,6,7,7-hexachloro-2-formylbicyclo[2.2.1]-5-heptene, 1,4,5,6,7,7-hexachloro-2-cyanobicyclo[2.2.1]-5-heptene, and hexachlorocyclopentenones. .Iadd. 
     
     
       18.  A composition comprising rubber and a flame-retarding agent selected from the group consisting of calcium mineral borate or a calcium metaborate and a halogen source, said halogen having an atomic weight greater than 19. .Iaddend. .Iadd. 
     
     
       19.  A composition according to claim 18, in which the calcium mineral borate or calcium metaborate is a natural mineral comprising a hydrated salt. .Iaddend. .Iadd. 
     
     
       20.  A composition according to claim 19, in which the inorganic compound is colemanite. .Iaddend. .Iadd.21. A composition according to claim 19, in which the inorganic compound is selected from ulexite and pandermite. 
     
     
        .Iaddend. .Iadd.22.  A composition according to claim 18, which contains calcium carbonate. .Iaddend. .Iadd.23. A composition according to claim 18 which is unfoamed. .Iaddend. .Iadd.24. A composition according to claim 18, which is foamed. .Iaddend. .Iadd.25. Carpet comprising a composition as claimed in claim 18 adhered to the undersurface of said carpet. 
     
     
        .Iaddend. .Iadd.26.  A composition of a normally flammable organic material selected from the group consisting of a polymer of an alpha olefin, a polyamide, a polyacetal, a polyurethane, a polyester, a rubber, rubber latex and an acrylic polymer, a calcium or magnesium mineral borate or a calcium or magnesium metaborate and a halogen source, said halogen 
     
     
        having an atomic weight greater than 19. .Iaddend. .Iadd.27.  A composition according to claim 26 wherein said mineral borate is a calcium borate. .Iaddend. .Iadd.28. A composition according to claim 27 wherein said borate is colemanite. .Iaddend. .Iadd.29. A composition according to 
     
     
        claim 26 wherein said mineral borate is a magnesium borate. .Iadd.30.  A composition according to claim 26 wherein the calcium mineral borate is selected from the group consisting of 2CaO.B 2  O 3 .H 2  O; CaO.B 2  O 3 .6H 2  O; CaO.B 2  O 3 .4H 2  O; CaO.B 2  O 3 .3.65H 2  O; 2CaO.3B 2  O 3 .H 2  O; 2CaO.3B 2  O 3 .13H 2  O; 2CaO.3B 2  O 3 .9H 2  O; 2CaO.3B 2  O 3 .7H 2  O; CaO.B 2  O 3 .2H 2  O; Colemanite, Sassolite, Ulexite, Tertschite, Probertite, Princeite, Pandermite, Inyoite, Meyerhofferite, Nobleite, Gowerite, Ginorite, Calciborite, K 2  O.CaO.4B 2  O 3 .12H 2  O; (NH 4 ) 2 .CaO.4B 2  O 3 .12H 2  O and Na 2  O.2CaO.5B 2  O 3 .16H 2  O. .Iaddend. .Iadd.31. A composition according to claim 30 wherein the calcium borate preferably has a negligable solubility in water at 25° C. .Iaddend. .Iadd.32. A composition according to claim 30 wherein the halogen source is selected from the group consisting of halogen-containing polymers, halogen-containing rubbers, halogen-containing phenolics, halogenated aliphatic compounds and halogenated aromatic compounds. .Iaddend. .Iadd.33. A composition according to claim 30 wherein the halogen source is selected from the group consisting of halogenated acids where the halogen is on a non-carbonyl atom, said acid having between 3 and 24 carbon atoms and being saturated or unsaturated, polyethers, ketones where at least one substituent attached to the carbonyl has between 4 and 12 carbon atoms, aldehydes where the substituent attached to the carbonyl group has between 4 and 12 carbon atoms, anhydrides of halogenated acids where the halogen is on a non-carbonyl atom and the group attached to the carbonyl atom has between 3 and 24 carbon atoms, primary alcohols in which the group attached to the OH radical has between 4 and 12 carbon atoms, secondary alcohols in which at least one group attached to the carbon atom to which the OH radical is attached has between 4 and 12 carbon atoms, acid halides of C 2  to C 12  atoms, monosaccharides, polysaccharides, starch, cellulose, esters of said acids, thio derivatives of said acids, aldehydes, ketones and alcohols where the sulfur atom replaces the oxygen atom, aryl compounds of C 6  to C 18  carbon atoms, aryl ethers where the organic group attached to the oxygen contains at least 4 carbon atoms, aryl aldehydes where the organic radical attached to the oxygen atom contains between 4 and 12 carbon atoms, arylketones where at one organic group attached to the oxygen atom has between 4 and 12 carbon atoms, alkenyl aryl compounds where the alkenyl group contains between 4 and 12 carbon atoms, aryl alcohols where at least one organic radical attached to the carbon bearing the hydroxy group has between 4 and 12 carbon atoms, hydroxy aryl compounds, sulfonated aryl compounds, nitrated aryl compounds, aryl acid halides of C 2  to C 12  atoms in the acid halide group, cyano aryl compounds, mercapto aryl compounds, amine aryl compounds, aromatic dicarboxylicacids and their anhydrides, cyclic and heterocyclic organic chemicals having between 5 and 10 members 
     
     
        in the ring. .Iaddend. .Iadd.34.  A composition according to claim 30 wherein said halogen source is selected from the group consisting of a compound having the formula ##STR4## its acids, mixed acids, bi-acids, mixed esters, bi-esters and anhydrides, wherein R can be H, C 1  -C 12  alkyl or a halogenated derivative thereof, 1,2,3,4-tetrachloro-5,5-dimethoxycyclopentadiene, 1,2,3,4-tetrachlorocyclopentadiene, nonachlorobicyclo[3.2.0]heptene-2, 1,2-dichloro-3,3,4,4,5,5-hexafluorocyclopentene, decachloropentacyclo[5.3.0.0 2 ,6.0 4 ,10.0 5 ,9 ]decan-3-one, octachlorocyclopentene, bis(pentachloro-2,4-cyclopentadiene-1-yl), 1,2,3,3,5,5-hexachloro-4-(dichloromethylene)-cyclopentene, perchloropentacyclo[5.2.1.0 2 ,6.0 3 ,9.0 5 ,8 ]-decane, 2,3,4,4,5-pentachloro-2-cyclopentene-1-one, 1,2,4-trichlorocyclopentene-3,5-dione, 1,2,3,4,7-hexachlorobicyclo[2.2.1]-2,5-heptadiene, 1,4,5,6,7,7-hexachlorobicyclo[2.2.1]-5-heptene-2,3-dicarboxylic acid, 1,4,5,6,7,7-hexachloro-2,3-bis(chloromethyl)-bicyclo[2.2.1]-5-heptene, 1,4,5,6,7,7-hexachloro-2-(1,2-dichloroethyl)-bicyclo[2.2.1]-5-heptene, 1,4,5,6,7,7-hexachloro-2-carboxybicyclo[2.2.1]-5-heptene, 1,4,5,6,7,7-hexachloro-2,3-bis(hydroxymethyl)-bicyclo[2.2.1]-5-heptene, undecachloropentacyclo[5.3.0 2 ,6.0 4 ,10.0 5 ,9 ]-3-decyclorosulfonate, 4,5,6,7,8,8-hexachloro-3a, 7a-dihydro-4,7-methano-indene, 1,2,3,4,10,10-hexachloro-1,4,4a,5,8,8a-hexahydro-1,4,-endo, exo-5,8-dimethanonaphthalene, 1,4,5,6,7,7-hexachloro-2-formylbicyclo[2.2.1]-5-heptene, 1,4,5,6,7,7-hexachloro-2-cyanobicyclo[2.2.1]-5-heptene, and 
     
     
        hexachlorocyclopentanones. .Iaddend. .Iadd.35.  A composition according to claim 32 wherein the mineral is present together with the halogen such that the weight ratio of mineral borate to halogen is between 1 and 8. .Iaddend. .Iadd.36. A composition according to claim 33 wherein the mineral is present together with the halogen such that the weight ratio of mineral borate to halogen is between 1 and 8. .Iaddend. .Iadd.37. A composition according to claim 36 wherein said ratio is between 1 and 4. 
     
     
        .Iaddend. .Iadd.38.  A composition of a normally flammable organic material comprising a vinyl polymer, a calcium or magnesium mineral borate or a calcium or magnesium metaborate and a halogen source, said halogen having an atomic weight greater than 19. .Iaddend.