CA1276388C - Flame retardant polyurethane foams - Google Patents
Flame retardant polyurethane foamsInfo
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- CA1276388C CA1276388C CA000511165A CA511165A CA1276388C CA 1276388 C CA1276388 C CA 1276388C CA 000511165 A CA000511165 A CA 000511165A CA 511165 A CA511165 A CA 511165A CA 1276388 C CA1276388 C CA 1276388C
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- flame retardant
- foam
- polyol
- phosphate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34922—Melamine; Derivatives thereof
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
FLAME RETARDANT POLYURETHANE FOAMS
Abstract of the Disclosure The invention pertains to flame retardant flexible polyurethane foams prepared by reacting a polyether polyol, an organic isocyanate, and a blowing agent incorporating (a) melamine in an amount ranging from about 30 weight percent to about 55 weight percent and an effective amount of (b) another flame retardant.
Abstract of the Disclosure The invention pertains to flame retardant flexible polyurethane foams prepared by reacting a polyether polyol, an organic isocyanate, and a blowing agent incorporating (a) melamine in an amount ranging from about 30 weight percent to about 55 weight percent and an effective amount of (b) another flame retardant.
Description
~ 3~ 88 FLAME RETARDANT POLYURETHANE FOAMS
sackground of the Invention 1. Field on the Invention The present invention pertains to flexible foam compositions and in particular to flexible polyurethane flame-retarded foam compositions and methods for the preparation thereof. More particularly, the present invention relates to the preparation of flexible poly-urethane flame-retarded foam compcsitions which contain an amount of melamine ranging from about 30 weight percent to about 55 weight percent of the total composition in con-junction with other flame retardant compounds.
sackground of the Invention 1. Field on the Invention The present invention pertains to flexible foam compositions and in particular to flexible polyurethane flame-retarded foam compositions and methods for the preparation thereof. More particularly, the present invention relates to the preparation of flexible poly-urethane flame-retarded foam compcsitions which contain an amount of melamine ranging from about 30 weight percent to about 55 weight percent of the total composition in con-junction with other flame retardant compounds.
2. Description of the Prior Art The preparation of flexible polyurethane flame-retardant foam compositions are generally well known as evidenced by the following prior art. U.S. 4,022,718 teaches the preparation of high resilience cold-cured p~lyurethane foams incorporating 2,3-dibromo-1,4-butenediol as a chain extender and flame-retardant component. U.S.
4,147,847 teaches a method of preparing flexible, flame-retarded, polyurethane foams by employing specific foam stabilizers which reduce the raquired amount of normal flame-retardant additives. U.S. 4,162,353 teaches the preparation of flexible polyurethane foams incorporating therein a halo-substituted alkyl phosphate such as, for ~ 2~d~388 example, tris(2-chlorethyl)-phosphate and an unsubstituted trialkylphosphate such as, for example, triethylphosphate.
The present invention is directed to preparing flame-retarded polyurethane foams which will pass both the Radiant Panel Flame Spread and the California 133 tests.
Summary of the Invention The present invention applies to both high-resiliency, flexible polyurethane foam compositions and conventional flexible polyurethane foam compositions which are prepared by the reaction of a polyoxyalkylene polyether polyol having at least two active hydrogen atoms and an average equivalent weight of from about 200 to about 2,500 with an organic polyisocyanate in the presence of ~a) melamine and an effective amount of (b) another flame retardant compound.
For a more complete understanding of the present invention, reference i9 made to the following detailed description and the examples thereof.
Descri~tion of the Preferred Embodiments It has unexpectedly been found that, in the preparation of flexible flame-retarded polyurethane foam, a mixture of (a) melamine and (b) an effective amount of another flame retardant cornpound incorporated into the polyoxyalkylene polyether polyol will result in foam which will pas~ both the Radiant Panel Test ASTM E162-81a and the California 133 test. It has been found that melamine i.n the amount ranging from about 30 weight percent to about 55 weight percent oE the total composition in combination with other flame retardants in the amount of about 1 weight percent to about 15 weight percent of the total composition will enable polyurethane foam to be prepared which will pass these tests.
Amond the flame retardant compounds in conjunction with melamine which may be employed are tetrakis(2-chloro-ethyl) ethylene phosphonate, pentabromodiphenyl oxide,tris(l,3-dichloropropyl) phosphate, tris(beta-chloroethyl) phosphate, molybdenum trioxide, ammonium molybdate, ammonium phosphate, pentabromodiphenyloxida, tricresyl phosphate, 2,3-dibromopropanol, hexabromocyclododecane, dibromoethyldi-bromocyclohexane, tris(2,3-dibromopropyl)phosphate, and tris(beta-chloropropyl)phosphate.
Representative polyols which may be employed in the preparation of the flame retardant p~lyurethane ~oams are well known to those skilled in the art. They are often prepared by the catalytic condensation of an alkylene oxide or mixture of alkylene oxides either simultaneously or sequentially with an organic compound having at least two active hydrogen atoms, such as evidenced by U.S. Patent Nos.
1,922,459, 3,190,927, and 3,346,557. Representative polyols include polyhydroxyl-containing polyesters, polyoxyalkylene 63~3 polyether polyols, polyhydroxy-terminated polyurethane polymers, polyhydroxyl-containing phosphorus compounds, and alkylene oxide adducts of polyhydric polythioesters, polyacetals, aliphatic polyols and thiols, ammonia, and amines including aromatic, aliphatic, and heterocyclic amines, as well as mixtures thereof. Alkylene oxide adducts of compounds which contain 2 or more different groups within the above-defined classes may also be used, for example, amino alcohols which contain an amino group and a hydroxyl group. Also, alkylene oxide adducts of compounds which contain one SH group and one OH group as well as those which contain an amino group and an SH group may be used.
Generally, the equivalent weight of the polyols will vary from 100 to 10,000, preferably from 200 to 2500.
Any suitable hydroxy-terminated polyester may be used such as are prepared, for example, from polycarboxylic acids and polyhydric alcohols. Any suitable polycarboxylic acid may be used such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, thapsic acid, maleic acid, fumaric acid, glutaconic acid, -hydro-muconic acid, ~ hydromuconic acid, -butyl--ethyl-glutaric acid, ~ diethylsuccinic acid, isophthalic acid, tere-phthalic acid, hemimellitic acid, and l,4-cyclohexanedi-carboxylic acid. Any suitable polyhydric alcohol, including 3~3 both aliphatic and aromatic, may be used such as ethylene glycol, propylene glycol, trimethylene glycol, l,2-butane-diol, 1,3-butanediol, 1,4~butanediol, 1,2-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptane-diol, glycerol, l,l,l-trimethylolpropane, l,l,l-trimethylol-ethane, lt2,6-hexanetriol, ~-methyl glucoside, penta-erythritol, and sorbitol. Also included within the term "polyhydric alcohol" are compounds derived from phenol such as 2,2-bis(4-hydroxyphenyl)propane, commonly known as Bisphenol A.
The hydroxyl-containing polyester may also be a polyester amide such as is obtained by including some amine or amino alcohol in the reactants Eor the preparation of the polyesterq. Thus, polyester amides may be obtained by condensing an amino alcohol such as ethanolamine with the polycarboxylic acids set forth above or they may be made using the same component~ that make up the hydroxyl-contain-ing polyester with only a portion of the components being a diamine such as ethylene diamine.
Any suitable polyoxyalkylene polyether polyol may be used such as the polymerization product of an alkylene oxide or a mixture of alkylene oxides with a polyhydric alcohol. Any suitable polyhydric alcohol may be used such as those disclosed above for use in the preparation of the hydroxy-terminated polyesters. Any suitable al~ylene oxide 3~3~
may be used such as ethylene oxide, propylene oxide, butylene oxide, amylene oxide, and mixtures of these oxides. The polyoxyalkylene polyether polyols may be prepared from other starting materials such as tetrahydro-furan and alkylene oxide~tetrahydrofuran mixtures; epihalo-hydrins such as epichlorohydrin, as well as aralkylene oxides such as styrene oxide. The polyoxyalkylene polyether polyols may have either primary or secondary hydroxyl groups. Included among the polyether polyols are polyoxy-ethylene glycol, polyoxypropylene glycol, polyoxybutylene glycol, polytetramethylene glycol, block copolymers, for example, combinations of polyoxypropylene and polyoxy-ethylene glycols, poly-1,2 oxybutylene and polyoxyethylene glycols, poly-1,4-oxybutylene and polyoxyethylene glycols, and random copolymer glycols prepared from blends of two or more alkylene oxides or by the sequential addition of two or more alkylene oxides. The polyoxyalkylene polyether polyols may be prepared by any known process such as, ~or example, the process disclosed by Wurtz in 1859 and Encyclo~oedia of Chemical Technology, Vol. 7, pp. 257~262, published by Interscience Publishers, Inc. (1951) or in U.S. Patent No. 1,922,459. Polyethers which are preferred include the alkylene oxide addition products of trimethylolpropane, glycerine, pentaerythritol, sucrose, sorbitol, propylene glycol, and 2,2'-~,4'-hydroxyphenyl)propane and blends thereof having equivalent weights of ~rom 100 to 10,000.
3~3~
Suitable polyhydric polythioethers which may be condensed with alkylene oxides include the condensation product of thiodiglycol or the reaction product of a dicarboxylic acid such as is disclosed above for the preparation of the hydroxyl-containing polyesters with any other suitable thioether glycol.
Polyhydroxyl-containing phosphorus compounds which may be used include those compounds disclosed in U.S. Patent No. 3,639,542. Preferred polyhydroxyl-containing phosphorus compounds are prepared from alkylene oxides and acids of phosphorus having a P2O5 equivalency of from about 72 percent to about 95 percent.
Suitable polyacetals which may be condensed with alkylene oxides include the reaction product of formaldehyde or other suitable aldehyde with a dihydric alcohol or an alkylene oxide such as those disclosed above.
Suitable aliphatic thiols which may be condensed with alkylene oxides include alkanethiols containing one or two -SH groups such as 2-mercaptoethanol, 1,2-ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, and 1,6-hexanedi-thiol, alkene thiols such as 2-butene-1,4-dithiol, and alkyne thiolq such a~ 3-hexyne-1,6-dithiol.
Suitable amines which may be condensed with alkylene oxides include aromatic amines such as aniline, o-chloroaniline, p-aminoaniline, 1,5-diaminonaphthalene, ~"~:~63~3 methylene dianlline, the condensation products of aniline and formaldehyde, and 2,3-, 2,6-, 3,4-, 2,5- and 2,4-diaminotoluene; aliphatic amines such as methylamine, triisopropanolamine, ethylenediamine, 1,3-diaminopropane, 1,3-diaminoblltane, 1,4-diaminobutane, and ammonia.
Also, polyols containing ester groups can be employed in the subject invention. These polyols are prepared by the reaction of an alkylene oxide with an organic dicarboxylic acid anhydride and a compound contain-ing reactive hydrogen atoms~ A more comprehensive discussion of these polyols and their method oE preparation can be found in U.S. Patents Nos. 3,585,185; 3,639,541 and 3,639,542.
Other polyols which may be employed have incorporated therein vinylic polymers. These polyols may be prepared (1) by the in situ free-radical polymerization of an ethylenically unsaturated monomer or mixture of monomers in a polyol, or (2~ by dispersion in a polyol of a preformed graft polymer prepared by free-radical polymerization in a solvent such as described in U.S. Patents 3,931,092;
4,147,847 teaches a method of preparing flexible, flame-retarded, polyurethane foams by employing specific foam stabilizers which reduce the raquired amount of normal flame-retardant additives. U.S. 4,162,353 teaches the preparation of flexible polyurethane foams incorporating therein a halo-substituted alkyl phosphate such as, for ~ 2~d~388 example, tris(2-chlorethyl)-phosphate and an unsubstituted trialkylphosphate such as, for example, triethylphosphate.
The present invention is directed to preparing flame-retarded polyurethane foams which will pass both the Radiant Panel Flame Spread and the California 133 tests.
Summary of the Invention The present invention applies to both high-resiliency, flexible polyurethane foam compositions and conventional flexible polyurethane foam compositions which are prepared by the reaction of a polyoxyalkylene polyether polyol having at least two active hydrogen atoms and an average equivalent weight of from about 200 to about 2,500 with an organic polyisocyanate in the presence of ~a) melamine and an effective amount of (b) another flame retardant compound.
For a more complete understanding of the present invention, reference i9 made to the following detailed description and the examples thereof.
Descri~tion of the Preferred Embodiments It has unexpectedly been found that, in the preparation of flexible flame-retarded polyurethane foam, a mixture of (a) melamine and (b) an effective amount of another flame retardant cornpound incorporated into the polyoxyalkylene polyether polyol will result in foam which will pas~ both the Radiant Panel Test ASTM E162-81a and the California 133 test. It has been found that melamine i.n the amount ranging from about 30 weight percent to about 55 weight percent oE the total composition in combination with other flame retardants in the amount of about 1 weight percent to about 15 weight percent of the total composition will enable polyurethane foam to be prepared which will pass these tests.
Amond the flame retardant compounds in conjunction with melamine which may be employed are tetrakis(2-chloro-ethyl) ethylene phosphonate, pentabromodiphenyl oxide,tris(l,3-dichloropropyl) phosphate, tris(beta-chloroethyl) phosphate, molybdenum trioxide, ammonium molybdate, ammonium phosphate, pentabromodiphenyloxida, tricresyl phosphate, 2,3-dibromopropanol, hexabromocyclododecane, dibromoethyldi-bromocyclohexane, tris(2,3-dibromopropyl)phosphate, and tris(beta-chloropropyl)phosphate.
Representative polyols which may be employed in the preparation of the flame retardant p~lyurethane ~oams are well known to those skilled in the art. They are often prepared by the catalytic condensation of an alkylene oxide or mixture of alkylene oxides either simultaneously or sequentially with an organic compound having at least two active hydrogen atoms, such as evidenced by U.S. Patent Nos.
1,922,459, 3,190,927, and 3,346,557. Representative polyols include polyhydroxyl-containing polyesters, polyoxyalkylene 63~3 polyether polyols, polyhydroxy-terminated polyurethane polymers, polyhydroxyl-containing phosphorus compounds, and alkylene oxide adducts of polyhydric polythioesters, polyacetals, aliphatic polyols and thiols, ammonia, and amines including aromatic, aliphatic, and heterocyclic amines, as well as mixtures thereof. Alkylene oxide adducts of compounds which contain 2 or more different groups within the above-defined classes may also be used, for example, amino alcohols which contain an amino group and a hydroxyl group. Also, alkylene oxide adducts of compounds which contain one SH group and one OH group as well as those which contain an amino group and an SH group may be used.
Generally, the equivalent weight of the polyols will vary from 100 to 10,000, preferably from 200 to 2500.
Any suitable hydroxy-terminated polyester may be used such as are prepared, for example, from polycarboxylic acids and polyhydric alcohols. Any suitable polycarboxylic acid may be used such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, thapsic acid, maleic acid, fumaric acid, glutaconic acid, -hydro-muconic acid, ~ hydromuconic acid, -butyl--ethyl-glutaric acid, ~ diethylsuccinic acid, isophthalic acid, tere-phthalic acid, hemimellitic acid, and l,4-cyclohexanedi-carboxylic acid. Any suitable polyhydric alcohol, including 3~3 both aliphatic and aromatic, may be used such as ethylene glycol, propylene glycol, trimethylene glycol, l,2-butane-diol, 1,3-butanediol, 1,4~butanediol, 1,2-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptane-diol, glycerol, l,l,l-trimethylolpropane, l,l,l-trimethylol-ethane, lt2,6-hexanetriol, ~-methyl glucoside, penta-erythritol, and sorbitol. Also included within the term "polyhydric alcohol" are compounds derived from phenol such as 2,2-bis(4-hydroxyphenyl)propane, commonly known as Bisphenol A.
The hydroxyl-containing polyester may also be a polyester amide such as is obtained by including some amine or amino alcohol in the reactants Eor the preparation of the polyesterq. Thus, polyester amides may be obtained by condensing an amino alcohol such as ethanolamine with the polycarboxylic acids set forth above or they may be made using the same component~ that make up the hydroxyl-contain-ing polyester with only a portion of the components being a diamine such as ethylene diamine.
Any suitable polyoxyalkylene polyether polyol may be used such as the polymerization product of an alkylene oxide or a mixture of alkylene oxides with a polyhydric alcohol. Any suitable polyhydric alcohol may be used such as those disclosed above for use in the preparation of the hydroxy-terminated polyesters. Any suitable al~ylene oxide 3~3~
may be used such as ethylene oxide, propylene oxide, butylene oxide, amylene oxide, and mixtures of these oxides. The polyoxyalkylene polyether polyols may be prepared from other starting materials such as tetrahydro-furan and alkylene oxide~tetrahydrofuran mixtures; epihalo-hydrins such as epichlorohydrin, as well as aralkylene oxides such as styrene oxide. The polyoxyalkylene polyether polyols may have either primary or secondary hydroxyl groups. Included among the polyether polyols are polyoxy-ethylene glycol, polyoxypropylene glycol, polyoxybutylene glycol, polytetramethylene glycol, block copolymers, for example, combinations of polyoxypropylene and polyoxy-ethylene glycols, poly-1,2 oxybutylene and polyoxyethylene glycols, poly-1,4-oxybutylene and polyoxyethylene glycols, and random copolymer glycols prepared from blends of two or more alkylene oxides or by the sequential addition of two or more alkylene oxides. The polyoxyalkylene polyether polyols may be prepared by any known process such as, ~or example, the process disclosed by Wurtz in 1859 and Encyclo~oedia of Chemical Technology, Vol. 7, pp. 257~262, published by Interscience Publishers, Inc. (1951) or in U.S. Patent No. 1,922,459. Polyethers which are preferred include the alkylene oxide addition products of trimethylolpropane, glycerine, pentaerythritol, sucrose, sorbitol, propylene glycol, and 2,2'-~,4'-hydroxyphenyl)propane and blends thereof having equivalent weights of ~rom 100 to 10,000.
3~3~
Suitable polyhydric polythioethers which may be condensed with alkylene oxides include the condensation product of thiodiglycol or the reaction product of a dicarboxylic acid such as is disclosed above for the preparation of the hydroxyl-containing polyesters with any other suitable thioether glycol.
Polyhydroxyl-containing phosphorus compounds which may be used include those compounds disclosed in U.S. Patent No. 3,639,542. Preferred polyhydroxyl-containing phosphorus compounds are prepared from alkylene oxides and acids of phosphorus having a P2O5 equivalency of from about 72 percent to about 95 percent.
Suitable polyacetals which may be condensed with alkylene oxides include the reaction product of formaldehyde or other suitable aldehyde with a dihydric alcohol or an alkylene oxide such as those disclosed above.
Suitable aliphatic thiols which may be condensed with alkylene oxides include alkanethiols containing one or two -SH groups such as 2-mercaptoethanol, 1,2-ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, and 1,6-hexanedi-thiol, alkene thiols such as 2-butene-1,4-dithiol, and alkyne thiolq such a~ 3-hexyne-1,6-dithiol.
Suitable amines which may be condensed with alkylene oxides include aromatic amines such as aniline, o-chloroaniline, p-aminoaniline, 1,5-diaminonaphthalene, ~"~:~63~3 methylene dianlline, the condensation products of aniline and formaldehyde, and 2,3-, 2,6-, 3,4-, 2,5- and 2,4-diaminotoluene; aliphatic amines such as methylamine, triisopropanolamine, ethylenediamine, 1,3-diaminopropane, 1,3-diaminoblltane, 1,4-diaminobutane, and ammonia.
Also, polyols containing ester groups can be employed in the subject invention. These polyols are prepared by the reaction of an alkylene oxide with an organic dicarboxylic acid anhydride and a compound contain-ing reactive hydrogen atoms~ A more comprehensive discussion of these polyols and their method oE preparation can be found in U.S. Patents Nos. 3,585,185; 3,639,541 and 3,639,542.
Other polyols which may be employed have incorporated therein vinylic polymers. These polyols may be prepared (1) by the in situ free-radical polymerization of an ethylenically unsaturated monomer or mixture of monomers in a polyol, or (2~ by dispersion in a polyol of a preformed graft polymer prepared by free-radical polymerization in a solvent such as described in U.S. Patents 3,931,092;
4,014,84 6; 4,093,573; and 4,122,05 6, or (3) by low temperature polymerization in the presence of chain transfer agents. These polymerizations may be carried out at a temperature between 65C and 170C, preferably between 75C
and 135C.
.' ' ~' ', "'' '' '. ''.
~.~7 Ei31~
The polyols which may be employed in the prepa-ration of the graft polymer dispersions are well known in the art. Both conventional polyols essentially free from ethylenic unsaturation such a~ those described in U.S.
Reissue Patent No. 28,715 and unsaturated polyols such a~
those described in U.S. Patent No. 3,652,659 and Reissue 29,014 may be employed in preparing the graft polymer dispersions used in the instant invention.
The polyurethane foams employed in the present invention are generally prepared by the reaction of a polyoxyalkylene polyether polyol with an organic polyiso-cyanate in the presence of a blowing agent and optionally in the presence of additional polyhydroxyl-containing compo-nents, chain-extending agents, catalysts, surface-active agents, ~tabilizers, dyes, fillers and pigments. Suitable proces~es ~or the preparation of cellular polyurethane ~oams a~e disclosed in U.S. Reissue Patent 24,~14 together with suitable machinery to be used in conjunction therewith.
When water i9 added as the blowing agent, corresponding quantities of excess isoc~ana~e to react with the water and produce carbon dioxide may be used. It i9 possible to proceed with the preparation of the polyurethane ~oams by a prepolymer technique wherein an excess o~ organic polyiso-cyanate i8 reacted in a fir~t step with the polyol of the ~ .
' present invention to prepare a prepolymer having free isocyanate groups which is then reacted in a second step with water and/or additional polyol to prepare a foam~
Alternatively, the components may be reacted in a single working step commonly known as the "one-shot" technique of preparing polyurethanes. Furthermore, instead of water, low boilin~ hydrocarbons such as pentane, hexane, heptane, pentene, and heptene, azo compounds such as azohexahydro-benzodinitrile, halogenated hydrocarbons such as dichlorodi-fluoromethane, trichlorofluoromethane, dichlorodifluoro-ethane, vinylidene chloride, and methylene chlori~e may be used as blowing agents.
Organic polyisocyanates which may be employed include aromatic, aliphatic, and cycloaliphatic polyiso-cyanates and combinations thereof. Representative of these types are the diisocyanates such as m-phenylene diiso-cyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, mixtures o~ 2,4- and 2,6-toluene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, cyclohexane-1,4-diisocyanate, hexahydrotoluene diisocyanate (and isomers),naphthalene-1,5-diisocyanate, 1-methoxyphenyl-2,4-diiso cyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate and 3,3'-dimethyl-diphenylmethane-4,4'-diisocyanate, the triisocyanates such 3~3 as 4,4',4"-triphenylmethane triisocyanate, and toluene 2,4,6-triisocyanate and the tetraisocyanates such as 4,4'-dimethyldiphenylmethane-2,2'-5,5'-tetraisocyanate and polymeric polyisocyanates such as polymethylene p~ly-phenylene polyisocyanate. Especially useful due to their availability and properties are toluene diisocyanate, 4,4'-diphenylmethane diisocyanate and polymethylene polyphenylene polyisocyanate. Toluene diisocyanate is preferred.
Crude polyisocyanates may also be used in the compositions of the present invention, such as crude toluene diisocyanate obtained by the phosgenation of a mixture of toluene diamines or crude diphenylmethane isocyanate obtained by the phosgenation of crude diphenylmethane diamine. The preferred or crude isocyanates are disclosed in U.S. Patent No. 3,215,652.
Chain-extending agents which may be employed in the preparation of the polyurethane foams include those compounds having at lea~t two functional groups bearing active hydrogen atoms such as water, hydrazine, primary and secondary diamines, amino alcohols, amino acids, hydroxy acids, glycols, or mixtures thereof. A preferred group of chain-extending agents includes water, ethylene glycol, 1,4-butanediol and primary and secondary diamine~ which react more readily with the prepolymer than does water such as phenylene dlamine, l,4-cyclohexane-bis-~methylamine), i3~33 ethylenediamine, diethylenetriamine, N-(2-hydroxypropyl)-ethylenediamine, N,N'-di(2-hydroxypropyl)ethylenediamine, pipera~ine, and 2-methylpiperazine.
Any suitable catalyst may be used including tertiary amines such as, for example, triethylenediamine, N-methylmorpholine, N-ethylmorpholine, diethylethanolamine, - N-cocomorpholine, l-methyl-~-dimethylaminoethylpiperazine, 3-mèthoxypropyldimethylamine, N,N,N'-trimethylisopropyl propylenediamine, 3-diethylaminopropyldiethylamine, di-methylbenzylamine, and the like. Other suitable catalysts are, for example, stannous chloride,dibutyltin di-2-ethyl hexanoate, stannous oxide, as well as other organometallic compounds such as are disclosed in U.S. Patent No.
2,846,408.
- A surface-active agent is generally necessary for ;production of high grade polyurethane foam accordin~ to the present invention, since in the absence of same, the foams collapse or contain very large uneven cells. Numerous surface-active agents have been found satisfactory.
Nonionic surface active agents are preferred. Of these, the nonionic surface-active agents such as the well-known silicones have been found particularly desirable. Other surface-active agents which are operative, although not preferred, include polyethylene glycol ethers of long chain alcohols, tertiary amine or alkanolamine salts of long chain ~.%~6~
alkyl acid sulfate e~ters, alkyl sulfonic esters, and alkyl arylsulfonic acids.
The following examples illustrate the nature of the invention. All parts are by weight unless otherwise stated. In the examples, the physical properties of the polyurethane foam were determined by the following ASTM
tests:
Density - D1622-63 Tensile Strength - D1623-72 Elongation - D412 Split Tear - D470 Compre~sion Set D395 Compression Load - D1554 Humid Aging - D1564 Additional tests included the California Bulletin No. 117 Test California 133 Test Radiant Panel Test ASTM E162-81a The following abbreviations are employed in the examples below:
Polyol A is a propylene oxida/ethylene oxide adduct of glycerine having a hydroxyl number of 35 and containing 16.5 percent ethylene oxide.
~.2'7~
Polyol B is a propylene oxide adduct of propylene glycol containing 50 percent of 2:1 styrene:acrylonitrile gra~t dispersion having a hydroxyl number of about 69.7.
Polyol C is a propylene oxide/ethylene oxide adduct of glycerine having a hydroxyl number of 56 and containing 9.0 percent ethylene oxide.
Polyol E i~ a propylene oxide adduct of a mixture of glycerine and propylene glycol having a hydroxyl number of 57.6.
Polyol F is a propylene oxide/ethylene oxide adduct of trimethylolpropane having a hydroxyl number of 25 and containing 15 percent ethylene oxide.
Polyol G is a propylene oxide adduct of propylene glycol having a hydroxyl number of 29 and containing 18 percent ethylene oxide.
Polyol H is a propylene oxide adduct of dipropylene glycol having a hydroxyl number of 29 and containing 18 ; percent ethylene oxide.
DEOA is diethanolamine.
TEOA is triethanolamine.
Silicone 5043 is a silicone surfactant manufactured by Dow Corning Corporation.
T-12 is dibutyltin dilaurate.
Frean 11 i9 mOnOElUrOtriChlOrOlnethane.
* Trade mark. - 14 -.
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Dabco 33LV is a 33 percent solution of triethylene diaminein dipropylene glycol.
Niax A-l is an amine catalyst manufactured by Union Carbon &
Carbide Corporation.
TDI is toluene diisocyanate.
Fyrol CEF is tris(beta-chloroethyl)phosphate.
DE60F i9 pentabromodiphenyl oxide.
Tharmolin 101 i9 tris~2,3-dibromopropyl)phosphate.
Fyrol PCF is tris(beta-chloropropyl)phosphate.
* Trade marks.
.
.
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~.%'7~3~
Examples 1-22 Examples 1-22 were prepared by employing the following procedure:
Blend A, composed of the polyol or polyol blend Fyrol CEF, Fyrol PCF or Thermolin 101, Freon 11, catalyst T-12, DEOA, and melamine in the proportions listed, was charged into a 150-qallon tank equipped with a turbine blade agitator turning at 100 rpm and agitated for about three houes at 72F. Blend B, composed of water, Dabco 33LV, NIAX
A-l and additional DEOA was charged into another tank.
Silicone surfactant DC-5043 was charged into a third tank and the TDI was charged into a fourth tank. These compo-nents were metered into a Hennecke UBT foam machine running with a mixer speed of 5000 rpm in the ratios of 82:1.5:0.5:13.6. The mixture was discharged from the mixing head unto a conveyoru The foam expanded to its full height in about three minutes. After a sufficient cure time the foams were submitted for physical property determinations.
. :
~%~63~r3 W IO O I I O O N ~ '~
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I Q a~ U ~ ~0 ~1 o ~ 0 1 ~ Q ~ H a ~12~ i38~3 Examples 23-28 The polyurethane foams of Table III were prepared by charging a one-quart cylindrical container with a suitable quantity of the polyol, water, catalysts, silicone surfactant and flame retardant compounds. The mixture was stirred for about 30 seconds, allowed to set for about 15 seconds and then stirring was resumed. After about 60 seconds elapsed time, the polyisocyanate was added to the container, and the resulting mixture was stirred for about 4 to 5 seconds. The content of the container was then immediately poured into a cardboard cake box, and the foam was allowed to rise therein. After the foam rise was completed, the resulting foam was oven cured for about 15 minutes.
Table III sets forth the ingredients and amounts thereof used to prepare the foams as well as the physical properties of the foams.
The flame retardancy tests, as exemplified by the Radiant Panel Test ASTkl E162-81a, indicate that flame retardancy may be obtained with a combination of melamine and other flame retardant compounds.
~.%~
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!!! I!!ill!li ~
rl ! i ! ! ! ! ! ! ! ~o~
! ! ! I ! ! I I I ! ! I ~ ~ r-l I, I I I I I I I 1 3 ~ o o ~
! ! ! ! ! ! ! ! ! ! ! ! ~ o h H ! ! 1l 1 ! ! ! ! ! ! ! ! ~ o ~ -~
H U~I O I ~ I I I I I I I I I ~ ' O h lilt~l ¦ I I I r~l I I I I I I I I I ~ O ~1 ,~ o ~;~I I I I o I I I I I I I I I I I r' ' ! ! ! ! ! ! ! ! ! ~ ~ h h oh h h ~
I I II a) I I I I ~9 u~ _I ~O h O O OI rl ~ rl I rl rl O N U7 0 ~;
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and 135C.
.' ' ~' ', "'' '' '. ''.
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The polyols which may be employed in the prepa-ration of the graft polymer dispersions are well known in the art. Both conventional polyols essentially free from ethylenic unsaturation such a~ those described in U.S.
Reissue Patent No. 28,715 and unsaturated polyols such a~
those described in U.S. Patent No. 3,652,659 and Reissue 29,014 may be employed in preparing the graft polymer dispersions used in the instant invention.
The polyurethane foams employed in the present invention are generally prepared by the reaction of a polyoxyalkylene polyether polyol with an organic polyiso-cyanate in the presence of a blowing agent and optionally in the presence of additional polyhydroxyl-containing compo-nents, chain-extending agents, catalysts, surface-active agents, ~tabilizers, dyes, fillers and pigments. Suitable proces~es ~or the preparation of cellular polyurethane ~oams a~e disclosed in U.S. Reissue Patent 24,~14 together with suitable machinery to be used in conjunction therewith.
When water i9 added as the blowing agent, corresponding quantities of excess isoc~ana~e to react with the water and produce carbon dioxide may be used. It i9 possible to proceed with the preparation of the polyurethane ~oams by a prepolymer technique wherein an excess o~ organic polyiso-cyanate i8 reacted in a fir~t step with the polyol of the ~ .
' present invention to prepare a prepolymer having free isocyanate groups which is then reacted in a second step with water and/or additional polyol to prepare a foam~
Alternatively, the components may be reacted in a single working step commonly known as the "one-shot" technique of preparing polyurethanes. Furthermore, instead of water, low boilin~ hydrocarbons such as pentane, hexane, heptane, pentene, and heptene, azo compounds such as azohexahydro-benzodinitrile, halogenated hydrocarbons such as dichlorodi-fluoromethane, trichlorofluoromethane, dichlorodifluoro-ethane, vinylidene chloride, and methylene chlori~e may be used as blowing agents.
Organic polyisocyanates which may be employed include aromatic, aliphatic, and cycloaliphatic polyiso-cyanates and combinations thereof. Representative of these types are the diisocyanates such as m-phenylene diiso-cyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, mixtures o~ 2,4- and 2,6-toluene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, cyclohexane-1,4-diisocyanate, hexahydrotoluene diisocyanate (and isomers),naphthalene-1,5-diisocyanate, 1-methoxyphenyl-2,4-diiso cyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate and 3,3'-dimethyl-diphenylmethane-4,4'-diisocyanate, the triisocyanates such 3~3 as 4,4',4"-triphenylmethane triisocyanate, and toluene 2,4,6-triisocyanate and the tetraisocyanates such as 4,4'-dimethyldiphenylmethane-2,2'-5,5'-tetraisocyanate and polymeric polyisocyanates such as polymethylene p~ly-phenylene polyisocyanate. Especially useful due to their availability and properties are toluene diisocyanate, 4,4'-diphenylmethane diisocyanate and polymethylene polyphenylene polyisocyanate. Toluene diisocyanate is preferred.
Crude polyisocyanates may also be used in the compositions of the present invention, such as crude toluene diisocyanate obtained by the phosgenation of a mixture of toluene diamines or crude diphenylmethane isocyanate obtained by the phosgenation of crude diphenylmethane diamine. The preferred or crude isocyanates are disclosed in U.S. Patent No. 3,215,652.
Chain-extending agents which may be employed in the preparation of the polyurethane foams include those compounds having at lea~t two functional groups bearing active hydrogen atoms such as water, hydrazine, primary and secondary diamines, amino alcohols, amino acids, hydroxy acids, glycols, or mixtures thereof. A preferred group of chain-extending agents includes water, ethylene glycol, 1,4-butanediol and primary and secondary diamine~ which react more readily with the prepolymer than does water such as phenylene dlamine, l,4-cyclohexane-bis-~methylamine), i3~33 ethylenediamine, diethylenetriamine, N-(2-hydroxypropyl)-ethylenediamine, N,N'-di(2-hydroxypropyl)ethylenediamine, pipera~ine, and 2-methylpiperazine.
Any suitable catalyst may be used including tertiary amines such as, for example, triethylenediamine, N-methylmorpholine, N-ethylmorpholine, diethylethanolamine, - N-cocomorpholine, l-methyl-~-dimethylaminoethylpiperazine, 3-mèthoxypropyldimethylamine, N,N,N'-trimethylisopropyl propylenediamine, 3-diethylaminopropyldiethylamine, di-methylbenzylamine, and the like. Other suitable catalysts are, for example, stannous chloride,dibutyltin di-2-ethyl hexanoate, stannous oxide, as well as other organometallic compounds such as are disclosed in U.S. Patent No.
2,846,408.
- A surface-active agent is generally necessary for ;production of high grade polyurethane foam accordin~ to the present invention, since in the absence of same, the foams collapse or contain very large uneven cells. Numerous surface-active agents have been found satisfactory.
Nonionic surface active agents are preferred. Of these, the nonionic surface-active agents such as the well-known silicones have been found particularly desirable. Other surface-active agents which are operative, although not preferred, include polyethylene glycol ethers of long chain alcohols, tertiary amine or alkanolamine salts of long chain ~.%~6~
alkyl acid sulfate e~ters, alkyl sulfonic esters, and alkyl arylsulfonic acids.
The following examples illustrate the nature of the invention. All parts are by weight unless otherwise stated. In the examples, the physical properties of the polyurethane foam were determined by the following ASTM
tests:
Density - D1622-63 Tensile Strength - D1623-72 Elongation - D412 Split Tear - D470 Compre~sion Set D395 Compression Load - D1554 Humid Aging - D1564 Additional tests included the California Bulletin No. 117 Test California 133 Test Radiant Panel Test ASTM E162-81a The following abbreviations are employed in the examples below:
Polyol A is a propylene oxida/ethylene oxide adduct of glycerine having a hydroxyl number of 35 and containing 16.5 percent ethylene oxide.
~.2'7~
Polyol B is a propylene oxide adduct of propylene glycol containing 50 percent of 2:1 styrene:acrylonitrile gra~t dispersion having a hydroxyl number of about 69.7.
Polyol C is a propylene oxide/ethylene oxide adduct of glycerine having a hydroxyl number of 56 and containing 9.0 percent ethylene oxide.
Polyol E i~ a propylene oxide adduct of a mixture of glycerine and propylene glycol having a hydroxyl number of 57.6.
Polyol F is a propylene oxide/ethylene oxide adduct of trimethylolpropane having a hydroxyl number of 25 and containing 15 percent ethylene oxide.
Polyol G is a propylene oxide adduct of propylene glycol having a hydroxyl number of 29 and containing 18 percent ethylene oxide.
Polyol H is a propylene oxide adduct of dipropylene glycol having a hydroxyl number of 29 and containing 18 ; percent ethylene oxide.
DEOA is diethanolamine.
TEOA is triethanolamine.
Silicone 5043 is a silicone surfactant manufactured by Dow Corning Corporation.
T-12 is dibutyltin dilaurate.
Frean 11 i9 mOnOElUrOtriChlOrOlnethane.
* Trade mark. - 14 -.
:' ~ .: .
~.~2'7~3~
Dabco 33LV is a 33 percent solution of triethylene diaminein dipropylene glycol.
Niax A-l is an amine catalyst manufactured by Union Carbon &
Carbide Corporation.
TDI is toluene diisocyanate.
Fyrol CEF is tris(beta-chloroethyl)phosphate.
DE60F i9 pentabromodiphenyl oxide.
Tharmolin 101 i9 tris~2,3-dibromopropyl)phosphate.
Fyrol PCF is tris(beta-chloropropyl)phosphate.
* Trade marks.
.
.
:, ' .
~.%'7~3~
Examples 1-22 Examples 1-22 were prepared by employing the following procedure:
Blend A, composed of the polyol or polyol blend Fyrol CEF, Fyrol PCF or Thermolin 101, Freon 11, catalyst T-12, DEOA, and melamine in the proportions listed, was charged into a 150-qallon tank equipped with a turbine blade agitator turning at 100 rpm and agitated for about three houes at 72F. Blend B, composed of water, Dabco 33LV, NIAX
A-l and additional DEOA was charged into another tank.
Silicone surfactant DC-5043 was charged into a third tank and the TDI was charged into a fourth tank. These compo-nents were metered into a Hennecke UBT foam machine running with a mixer speed of 5000 rpm in the ratios of 82:1.5:0.5:13.6. The mixture was discharged from the mixing head unto a conveyoru The foam expanded to its full height in about three minutes. After a sufficient cure time the foams were submitted for physical property determinations.
. :
~%~63~r3 W IO O I I O O N ~ '~
oo ~ o ~ ~1 0 ~ O O
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H
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~1 ~ o o ~ c~ ~ ~ o o ~ o ~
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I I I u~ O o I ~i o u~ ~i o o ~' ~ ~ .
c l ~ ~ c .
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0 ~ ~
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U
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~ ~ ~ .
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1~ ~ t~
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3~
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o ~ ~ o ~ ~ U~
-~ ~ o o '`I ' ' ' o ~ S o ~
H I ,_1 0 0 ~,~
O O I I I O O U~ ~ _~ C~ ~ ~ ~ I I ~ I I
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E-l ~ ~ O o u~l o o I I I o o ~ ~ ~ o ~ ~ ~ I I ~ I I
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I Q a~ U ~ ~0 ~1 o ~ 0 1 ~ Q ~ H a ~12~ i38~3 Examples 23-28 The polyurethane foams of Table III were prepared by charging a one-quart cylindrical container with a suitable quantity of the polyol, water, catalysts, silicone surfactant and flame retardant compounds. The mixture was stirred for about 30 seconds, allowed to set for about 15 seconds and then stirring was resumed. After about 60 seconds elapsed time, the polyisocyanate was added to the container, and the resulting mixture was stirred for about 4 to 5 seconds. The content of the container was then immediately poured into a cardboard cake box, and the foam was allowed to rise therein. After the foam rise was completed, the resulting foam was oven cured for about 15 minutes.
Table III sets forth the ingredients and amounts thereof used to prepare the foams as well as the physical properties of the foams.
The flame retardancy tests, as exemplified by the Radiant Panel Test ASTkl E162-81a, indicate that flame retardancy may be obtained with a combination of melamine and other flame retardant compounds.
~.%~
CDI I I I ~ O I I I I ~ I I I I I ~ ' ~
!!! I!!ill!li ~
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H U~I O I ~ I I I I I I I I I ~ ' O h lilt~l ¦ I I I r~l I I I I I I I I I ~ O ~1 ,~ o ~;~I I I I o I I I I I I I I I I I r' ' ! ! ! ! ! ! ! ! ! ~ ~ h h oh h h ~
I I II a) I I I I ~9 u~ _I ~O h O O OI rl ~ rl I rl rl O N U7 0 ~;
N`o ~ ~i 0 0 ~ O O ~ ~ ~ ~ h h al r-l r 1 0 1~ ~
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r~ ~ ~
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~ h r-l r-l r l h h a~ r~l O r-l r-l (~ C
x o o o o ~ a~ 0 ~ a o a~ x ~
~, ~ ~ ~ ~ a~: a v~ a z~ ~ O ~ * * *
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.
:: , - . .
. :, .
i3~
The ASTM E162-81a radiant panel test requires a figure of less than 100 to pass the test. The California 133 test is rated in "pass" or "fail" terms. The California 133 test is done on both covered and uncovered specimines.
In the following Examples the covering employed was ~odacrylic/nylon fabric. In Example 8, 17, 18, and 19, Fyrol CEF was replaced with DE-60~. The results of Tables y I, III and III indicate that a combination of melamine and other flame retardants are required to pass the radiant panel test and the California 133 test.
Examples 29-31 Examples 29-31 were prepared in a manner similar to that employed for Examples 23-28. The Examples of Table IV indicate that amounts of melamine in excess of 55 percent result in foams having deteriorating and unaccept-able physical properties.
* a trade mark for pentabromodiphenyl oxide ~'~
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I I I I I I I I I I ~1 O I I I I I I I I I I
t~ I I I 1~ I r1 1 1 1 1 1 I d' CO O O
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The ASTM E162-81a radiant panel test requires a figure of less than 100 to pass the test. The California 133 test is rated in "pass" or "fail" terms. The California 133 test is done on both covered and uncovered specimines.
In the following Examples the covering employed was ~odacrylic/nylon fabric. In Example 8, 17, 18, and 19, Fyrol CEF was replaced with DE-60~. The results of Tables y I, III and III indicate that a combination of melamine and other flame retardants are required to pass the radiant panel test and the California 133 test.
Examples 29-31 Examples 29-31 were prepared in a manner similar to that employed for Examples 23-28. The Examples of Table IV indicate that amounts of melamine in excess of 55 percent result in foams having deteriorating and unaccept-able physical properties.
* a trade mark for pentabromodiphenyl oxide ~'~
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a~
,~
rlA ~ ~ 1~ A A A ~ ~ A A O
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I I I I I I I I I I E~
l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l I I I I I I I I I I
l l l l l l l l l l I I I I I I I I I I
I I I I I I I I I I ~1 O I I I I I I I I I I
t~ I I I 1~ I r1 1 1 1 1 1 I d' CO O O
I I ~ t~ I I I I ,1 1 1 I I I r~ I I I I I ~ I
:~
~ I I II I I I I I I
~ I I II I I I I I I
E~ I I II I I I I I I
I
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l l l l l l l l l l I I I I I I I I I I
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æ
Claims (6)
1. In the preparation of a flame retardant flexible polyurethane foam prepared by the reaction of a polyoxyalkylene polyether polyol having an average equiva-lent weight of from about 200 to about 2500, an organic polyisocyanate and a blowing agent, the improvement which comprises incorporating into the polyether polyol (a) melamine in the amount ranging from about 30 weight percent to about 55 weight percent of the total composition and an effective amount of (b) another flame retardant.
2. The foam of claim 1 wherein flame retardant (b) is employed in the amount of about 1 weight percent to about 15 weight percent of the total composition.
3. The foam of claim 1 wherein the polyether polyol is a blend of a propylene oxide, ethylene oxide adduct of glycerine containing about 17 weight percent ethylene oxide and a propylene oxide adduct of propylene glycol containing about 50 weight percent of a 2:1 styrene acrylonitrile graft dispersion.
4. The foam of claim 3 wherein the glycerine based polyol is about 91.5 weight percent of the polyol blend.
5. The foam of claim 1 wherein the amount of melamine ranges from about 40 to about 45 weight percent of the total composition
6. The foam of claim 1 wherein flame retardant (b) is selected from the group consisting of tris (2-chloroethyl) phosphate, tris(2-chloropropyl) phosphate, pentabromodiphenyl oxide and tris (2,3-dibromopropyl) phosphate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US74995785A | 1985-06-27 | 1985-06-27 | |
| US749,957 | 1985-06-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1276388C true CA1276388C (en) | 1990-11-13 |
Family
ID=25015931
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000511165A Expired - Fee Related CA1276388C (en) | 1985-06-27 | 1986-06-09 | Flame retardant polyurethane foams |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS6248717A (en) |
| AU (1) | AU588604B2 (en) |
| CA (1) | CA1276388C (en) |
| GB (1) | GB2177406B (en) |
| MX (1) | MX168346B (en) |
| NZ (1) | NZ216580A (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8421967D0 (en) * | 1984-08-30 | 1984-10-03 | Hickory Springs Mfg Co | Polyurethane foams |
| IT1185558B (en) * | 1985-04-30 | 1987-11-12 | Himont Inc | POLYMERIC COMPOSITIONS EQUIPPED WITH IMPROVED FLAME RESISTANCE CHARACTERISTICS |
| BR8807513A (en) * | 1987-05-21 | 1990-03-27 | Reeves Bros Inc | POLYURETHANE FOAM FORMING COMPOSITION DERIVED FROM FLEXIBLE POLYETHER, FLEXIBLE POLYURETHANE FOAM, AND PROCESSES FOR FAST CURE AND IMPROVEMENT OF DEFORMATION PROPERTIES BY COMPRESSION OF A POLYETER DERIVED FOAM, FERTAINED, AND FLEXIBLE DETERMINATIONS. |
| US4826884A (en) * | 1987-07-20 | 1989-05-02 | Basf Corporation | Flame retardant polyurethane foams resistant to cigarette smoldering ignition |
| JP2654651B2 (en) * | 1987-12-25 | 1997-09-17 | 株式会社イノアックコーポレーション | Method for producing high hardness and flame retardant flexible polyurethane slab foam with low compression set |
| DE3829958A1 (en) * | 1988-09-03 | 1990-03-08 | Bayer Ag | METHOD FOR PRODUCING POLYURETHANE FOAMS |
| DE3842385A1 (en) * | 1988-12-16 | 1990-07-12 | Bayer Ag | METHOD FOR PRODUCING POLYURETHANE FOAMS |
| DE3842384A1 (en) * | 1988-12-16 | 1990-07-12 | Bayer Ag | METHOD FOR PRODUCING POLYURETHANE FOAMS |
| AT394049B (en) * | 1989-04-04 | 1992-01-27 | Chemie Linz Gmbh | MELAMINE PREPARATION, STABLE DISPERSION OF MELAMINE IN POLYETHEROLS, METHOD FOR THE PRODUCTION AND THEIR USE |
| DE4010752A1 (en) * | 1990-04-03 | 1991-10-10 | Metzeler Schaum Gmbh | METHOD FOR PRODUCING A FLAME-RESISTANT, ELASTIC POLYURETHANE-SOFT FOAM |
| US8048935B2 (en) | 2004-11-08 | 2011-11-01 | Carpenter Co. | Liquid foam systems and ASTM E-84 class 1 rated rigid, high-density polyurethane foams and articles prepared therefrom |
| EP2209827B1 (en) * | 2007-11-14 | 2016-05-25 | Basf Se | Foamed polyurethanes having improved flexural endurance properties |
| CN111363135B (en) * | 2020-03-14 | 2022-11-08 | 浙江恒丰新材料有限公司 | Preparation method and application of melamine-ethylene oxide/propylene oxide copolymer polyether polyol |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5238880B2 (en) * | 1974-12-25 | 1977-10-01 | ||
| JPS5232917B2 (en) * | 1974-12-25 | 1977-08-24 | ||
| JPS53106799A (en) * | 1977-03-02 | 1978-09-18 | Bridgestone Corp | Synthetic resin form and its preparation |
| DE2815554A1 (en) * | 1978-04-11 | 1979-10-25 | Basf Ag | FLAME RESISTANT SOFT POLYURETHANE FOAM |
| DE2932304A1 (en) * | 1979-08-09 | 1981-02-26 | Basf Ag | STABLE FILLER-POLYOL DISPERSIONS, A METHOD FOR THE PRODUCTION THEREOF AND THE USE FOR THE PRODUCTION OF POLYURETHANE PLASTICS, WHICH MAY BE FOAMED |
| DE3100626C2 (en) * | 1981-01-12 | 1985-05-15 | Schmittmann, Hans-Bernd, Dipl.-Chem. Dr.Rer.Nat., 5620 Velbert | Flame-retardant plastics, especially those which can be used as building materials or the like, processes for their production and their use as components |
| GB8421967D0 (en) * | 1984-08-30 | 1984-10-03 | Hickory Springs Mfg Co | Polyurethane foams |
-
1986
- 1986-05-15 GB GB8611884A patent/GB2177406B/en not_active Expired
- 1986-06-09 CA CA000511165A patent/CA1276388C/en not_active Expired - Fee Related
- 1986-06-18 NZ NZ21658086A patent/NZ216580A/en unknown
- 1986-06-24 AU AU59264/86A patent/AU588604B2/en not_active Ceased
- 1986-06-26 MX MX294086A patent/MX168346B/en unknown
- 1986-06-27 JP JP61151286A patent/JPS6248717A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| GB8611884D0 (en) | 1986-06-25 |
| GB2177406A (en) | 1987-01-21 |
| MX168346B (en) | 1993-05-19 |
| AU5926486A (en) | 1987-01-08 |
| JPS6248717A (en) | 1987-03-03 |
| AU588604B2 (en) | 1989-09-21 |
| NZ216580A (en) | 1989-10-27 |
| GB2177406B (en) | 1989-07-12 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |