CA1225485A - Process for the preparation of white graft polymer dispersions and flame-retardant polyurethane foams - Google Patents
Process for the preparation of white graft polymer dispersions and flame-retardant polyurethane foamsInfo
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- CA1225485A CA1225485A CA000448076A CA448076A CA1225485A CA 1225485 A CA1225485 A CA 1225485A CA 000448076 A CA000448076 A CA 000448076A CA 448076 A CA448076 A CA 448076A CA 1225485 A CA1225485 A CA 1225485A
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Abstract
PROCESS FOR THE PREPARATION OF WHITE GRAFT POLYMER DISPERSIONS AND FLAME RETARDANT POLYURETHANE FOAMS White graft polymer dispersions in polyoxyalkylene polyether polyols are employed together with flame retardant compounds to prepare flame retardant polyurethane foams. The polymer dispersions employ less than 0.1 mole of induced unsaturation per mole of polyol mixture. Improved processes for the reparation of these polymer dispersions employ either isomerized maleate containing polyetherester polyols or polyetherester polyols prepared by reacting a polyoxyalkylene polyether polyol, a polycarboxylic acid anhydride and an alkylene oxide in the presence of salts and oxides of divalent metals.
Description
s BacX~ound of the Invention l. Field of the Invention The present invention relates to low viscosity white graft polymer dispersions in po1yoxyalkylene polyether polyols and flame retardant polyurethane foams prepared therefrom. Dispersions of this type are also dealt with in co~pending Canadian application no. 424,626. More particu-larly, the invention relates to graft polymer dispersions prepared by the improved process employing free radical polymerization of an ethylenically unsaturated monomer or mixture of monomers in a polyol mixture containing less than O.l mole of induced unsaturation per mole of polyol mixture.
This improved process yields stable, non-settling dispersions with graft polymer contents of 30 percent by weight and higher employing monomer mixtures which contain more than about 55 percent by weight styrene as the comonomer. Furtherl the invention relates to an improved process employing free radical polymerization in a polyetherester polyol-polyoxy-alkylene polyether polyol mixture containing less than O.l mole of induced unsaturation per mole of polyol mixture wherein the unsaturated moiety is an isomerized maleate containing polyetherester polyol. Even more particularly the invention relates to an improved process employing free radical polymerization in a polyol mixture containing polyetherester polyol-polyoxyalkylene polyether polyol mixture which was S';L~5 prepared by reactiny a polyoxyalkylene polyether polyol, a polycarboxylic acid anhydrlde and an alkylene oxide in the presence of an effective amount of a catalyst selected fxom the group consisting of salts and oxides of divalent metals.
20 Description of the Prior Art The prior art, as evidenced by U.S. Patent Nos.
3,652,658; 3,875,258; 3,950,317, and Reissue Patent Nos.
28,715 and 29,014 teaches the preparation of graft polymer dispersions which are useful in the preparation of poly-urethanes by the polymerization of ethylenically unsaturatedmonomers in the presence of polyols. The above patents disclose various methods of preparing graft polymer disper-sions. U.S. 3,931,092 teaches the preparation of polymeric solids by polymerizing in the presence of a free-radical initiator and an organic solvent. The solvent concentration employed is from about 1 part to 19 parts by weight per part of the hydroxy-terminated organic compound which has a polymerizable carbon double bond. U.SO 3,953,393 teaches the preparation of graft copolymer dispersions by employing alkylmercaptan chain transferring agents at concentrations from 0.1 to 2 percent by weigh~ based on the weight of vinyl monomer.
Stable dispersions of polymers in polyols have found broad commercial use in the preparation of poly-urethanes. The use of these dispersions, known in the tradeas graft or polymer polyols, improves processing and, among other properties, the firmness of the polyurethane products, often expressed as load bearing or modulus. There have been many attempts to improve the products representing the present state of the art~ Efforts have been directed towards increasing the amount of polymer which is dispersed in the polyol, the obvious benefit being that firmer polyurethanes can be produced. Two major obstacles have been found: the viscosities of the resulting dispersions were too high and/or relatively high levels of acrylonitrile had to be used in the monomer mixtures employedO
The use of high levels (> 50 percent by weight) of acrylonitrile and, correspondingly, relatively low levels of the most common comonomer, styrene (< 50 percent) had two very undesirable effects. The resulting dispersions are tan to ~rown in color with a strong tendency to turn even darker in color during the highly exothermic polyurethane foam formation giving, for example, slab foams with a strong tendency to scorch. But even more undesirable, polyurethane foams made from these products cannot be satisfactorily flame retarded to pass flammability tests which are standard in the industryO
As mentioned before, there have been attempts to prepare high polymer (> 30 percent) containing dispersions 4~i with acceptable viscosities. These products contain ratios of acrylonitrile to styrene of >50/50 and are tan colored.
None of the prior art teaches that polymer dispersions in unsaturated polyols containing less than 0.1 mole oE induced unsaturation per mole of polyol mixture may be employed for flame-retardant polyurethane foams. Neither has the prior art taught that in situ free radical polymerizations may be conducted in a polyetherester polyol-polyoxyalkylene polyether polyol mixture containing less than 0.1 mole of induced unsaturation per mole of polyol mixture wherein the unsaturated moiety is an isomerized maleate containing polyetherester polyol. Also, the prior art is silent on the preparation of polyetherester polyols, by the reaction of a polyoxyalkylene polyether polyol, a polycarboxylic acid anhydride, and an alkylene oxide, in the presence of a catalyst selected from the group consisting of salts and oxides of divalent metals.
Summary of the Invention It has been discovered that flamè-retardant polyurethane foams may be prepared by employing gra~t polymer dispersions. These dispersions are prepared by an improved process employing free radical polymerization of ethylenically unsaturated monomer or monomers in a polyol mixture containing less than 0.1 mole of induced unsatura-tion per mole of polyol mixture. Furthermore, it has been iiiLI~S
found that improved dispersions may be prepared by employing radical polymerization in a polyetherester polyol-polyoxy-alkylene polyether polyol mixture containing less than 0.1 mole of induced unsa~uration per mole of polyol mixture wherein the unsaturation moiety is an isomerized maleate containing polyetherester polyol. Still furthermore, it has been found that improved dispersions may be prepared by conducting the free radical polymerization in the presence of a polyetherester polyol which was prepared by reacting a polyether polyol, a polycarboxylic acid anhydride, and an alkylene oxide in the presence of an effective amount of a catalyst selected from the qroup consisting of salts and oxides of divalent metals.
Description of the Preferred Embodiments In accordance with the improved process for the preparation of white graft polymer dispersions which are employed for the preparation of flame-retardant polyurethane foams, the improvement comprises conducting the polymeriza-tion of an ethylenically unsaturated monomer or mixtures of monomers in the presence of an effective amount of a free-radical initiator in an unsaturated polyol mixture con-taining less than 0.1 mole of induced unsaturation per mole of polyol mixture. In another embodiment of the invention the polymerization of an ethylenically unsaturated monomer or mixture of monomers in the presence of an effective 5~
amount of a free radical initiator in an unsaturation containing polyol mixture containing less than 0.1 mole of unsaturation per mole of polyol mixture employs an improved process which comprises conduc~ing the polymerization in a polyol mixture employing as part of the mixture a polyether-ester polyol prepared by the reaction of a polyoxyalkylene polyether polyol with maleic anhydride and an alkylene oxide. This polyetherester polyol is isomerized by methods well known by those skilled in the art. These include heat, or isomerization catalysts such as morpholine, dibutylamine, diethylamine, diethanolamine, thiols and the like. In another improved process for the preparation of these graft polymer dispersions, the improvement consists of preparing a polyetherester polyol by the reaction of a polyoxyalkylene ether polyol, a polycarboxylic acid anhydride to form a half acid ester and an alkylene oxide to obtain a product having an acid number of less than 5 mg KOH/gram which cornprises conducting the reaction between the polyoxyalkylene poly-ether polyol and the anhydride and the following reaction with the alkylene oxide in the presence of an effective amount of a catalyst selected from the group consisting of salts and oxides of divalent metals. The polyols having induced unsaturation are hereinafter referred to as ~Imacro-mers." Chain transfer agents may be employed as reaction moderators particularly at temperatu-res below 105C. The s~s polymerization reaction may be carried out at temperatures between 25C and 180C, preferably between 80C and 135C~
The polyol mixture contains less than 0.1 mole o~ unsatura-tion per mole of polyol mixture and ranges from 0.001 to 0.09 mole of unsaturation~
The alkylene oxides which may be employed for ~he preparation of the polyetherester polyols include ethylene oxide, propylene oxide, butylene oxide, amylene oxide and mixtures of these oxides~
The graft polymer dispersions of this invention have viscosities less than 10,000 cps at 25C. Preferably they have viscosities ranging from 2000 to 8000 cps at 25C.
Among those chain transfer agents which may be employed are as follows: acetic acid, bromoacetic acid, chloroacetic acid, ethyl dibromoacetate, iodoacetic acid, tribromoacetic acid, ethyl tribromoacetate, trichloroacetic acid, ethyl trichloroacetate, acetone, p-bromophenylaceto-nitrile, p-nitrophenylacetylene, allyl alcohol, 2,4,6-trinitroaniline, p-ethynylanisole, 2,4,6-trinitroanisole, azobenzene, benzaldehyde, p-cyanobenzaldehyde, 2-butyl-benzene, bromobenzene, 1,3,5-trinitrobenzene, benzochrysene, ethyl trinitrobenzoate, benzoin, benzonitrile, benzopyrene, tributylborane, 1,4-butanediol, 3,4-epoxy-2-methyl-1-butene, t-butyl ether, t-butyl isocyanide, l-phenylbutyne, p-cresol, p-bromocumene, dibenzonaphthacene, p-dioxane, pentaphenyl ~,~2S4~5 ethane, ethanol, l,l-diphenylethylene, ethylene glycol, ethyl ether, ~luorene, N,N dimethylformamide, 2-heptene, 2-hexe~e, isobutyraldehyde, diethyl bromomalonate, bromotri-chloromethane, dibromoethane, diiodomethane, naphthalene, 1-naphthol, 2-napthol, methyl oleate, 2,4,4-triphenyl-1-pentene, 4-methyl-2-pentene, 2,6-diisopropylphenol, phenyl etherl phenylphosphine, diethylphosphine, dibutylphosphine, phosphorus trichloride, l,l,l-tribromopropane, dialkyl phthalate, 1,2-propanediol, 3-phosphinopropionitrile, 1-propanol, pyrocatechol, pyrogallol, methyl stearate,tetraethylsilane, triethylsilane, dibromostilbene, a~
bromostyrene, ~-methylstyrenel tetraphenyl succinonitrile,
This improved process yields stable, non-settling dispersions with graft polymer contents of 30 percent by weight and higher employing monomer mixtures which contain more than about 55 percent by weight styrene as the comonomer. Furtherl the invention relates to an improved process employing free radical polymerization in a polyetherester polyol-polyoxy-alkylene polyether polyol mixture containing less than O.l mole of induced unsaturation per mole of polyol mixture wherein the unsaturated moiety is an isomerized maleate containing polyetherester polyol. Even more particularly the invention relates to an improved process employing free radical polymerization in a polyol mixture containing polyetherester polyol-polyoxyalkylene polyether polyol mixture which was S';L~5 prepared by reactiny a polyoxyalkylene polyether polyol, a polycarboxylic acid anhydrlde and an alkylene oxide in the presence of an effective amount of a catalyst selected fxom the group consisting of salts and oxides of divalent metals.
20 Description of the Prior Art The prior art, as evidenced by U.S. Patent Nos.
3,652,658; 3,875,258; 3,950,317, and Reissue Patent Nos.
28,715 and 29,014 teaches the preparation of graft polymer dispersions which are useful in the preparation of poly-urethanes by the polymerization of ethylenically unsaturatedmonomers in the presence of polyols. The above patents disclose various methods of preparing graft polymer disper-sions. U.S. 3,931,092 teaches the preparation of polymeric solids by polymerizing in the presence of a free-radical initiator and an organic solvent. The solvent concentration employed is from about 1 part to 19 parts by weight per part of the hydroxy-terminated organic compound which has a polymerizable carbon double bond. U.SO 3,953,393 teaches the preparation of graft copolymer dispersions by employing alkylmercaptan chain transferring agents at concentrations from 0.1 to 2 percent by weigh~ based on the weight of vinyl monomer.
Stable dispersions of polymers in polyols have found broad commercial use in the preparation of poly-urethanes. The use of these dispersions, known in the tradeas graft or polymer polyols, improves processing and, among other properties, the firmness of the polyurethane products, often expressed as load bearing or modulus. There have been many attempts to improve the products representing the present state of the art~ Efforts have been directed towards increasing the amount of polymer which is dispersed in the polyol, the obvious benefit being that firmer polyurethanes can be produced. Two major obstacles have been found: the viscosities of the resulting dispersions were too high and/or relatively high levels of acrylonitrile had to be used in the monomer mixtures employedO
The use of high levels (> 50 percent by weight) of acrylonitrile and, correspondingly, relatively low levels of the most common comonomer, styrene (< 50 percent) had two very undesirable effects. The resulting dispersions are tan to ~rown in color with a strong tendency to turn even darker in color during the highly exothermic polyurethane foam formation giving, for example, slab foams with a strong tendency to scorch. But even more undesirable, polyurethane foams made from these products cannot be satisfactorily flame retarded to pass flammability tests which are standard in the industryO
As mentioned before, there have been attempts to prepare high polymer (> 30 percent) containing dispersions 4~i with acceptable viscosities. These products contain ratios of acrylonitrile to styrene of >50/50 and are tan colored.
None of the prior art teaches that polymer dispersions in unsaturated polyols containing less than 0.1 mole oE induced unsaturation per mole of polyol mixture may be employed for flame-retardant polyurethane foams. Neither has the prior art taught that in situ free radical polymerizations may be conducted in a polyetherester polyol-polyoxyalkylene polyether polyol mixture containing less than 0.1 mole of induced unsaturation per mole of polyol mixture wherein the unsaturated moiety is an isomerized maleate containing polyetherester polyol. Also, the prior art is silent on the preparation of polyetherester polyols, by the reaction of a polyoxyalkylene polyether polyol, a polycarboxylic acid anhydride, and an alkylene oxide, in the presence of a catalyst selected from the group consisting of salts and oxides of divalent metals.
Summary of the Invention It has been discovered that flamè-retardant polyurethane foams may be prepared by employing gra~t polymer dispersions. These dispersions are prepared by an improved process employing free radical polymerization of ethylenically unsaturated monomer or monomers in a polyol mixture containing less than 0.1 mole of induced unsatura-tion per mole of polyol mixture. Furthermore, it has been iiiLI~S
found that improved dispersions may be prepared by employing radical polymerization in a polyetherester polyol-polyoxy-alkylene polyether polyol mixture containing less than 0.1 mole of induced unsa~uration per mole of polyol mixture wherein the unsaturation moiety is an isomerized maleate containing polyetherester polyol. Still furthermore, it has been found that improved dispersions may be prepared by conducting the free radical polymerization in the presence of a polyetherester polyol which was prepared by reacting a polyether polyol, a polycarboxylic acid anhydride, and an alkylene oxide in the presence of an effective amount of a catalyst selected from the qroup consisting of salts and oxides of divalent metals.
Description of the Preferred Embodiments In accordance with the improved process for the preparation of white graft polymer dispersions which are employed for the preparation of flame-retardant polyurethane foams, the improvement comprises conducting the polymeriza-tion of an ethylenically unsaturated monomer or mixtures of monomers in the presence of an effective amount of a free-radical initiator in an unsaturated polyol mixture con-taining less than 0.1 mole of induced unsaturation per mole of polyol mixture. In another embodiment of the invention the polymerization of an ethylenically unsaturated monomer or mixture of monomers in the presence of an effective 5~
amount of a free radical initiator in an unsaturation containing polyol mixture containing less than 0.1 mole of unsaturation per mole of polyol mixture employs an improved process which comprises conduc~ing the polymerization in a polyol mixture employing as part of the mixture a polyether-ester polyol prepared by the reaction of a polyoxyalkylene polyether polyol with maleic anhydride and an alkylene oxide. This polyetherester polyol is isomerized by methods well known by those skilled in the art. These include heat, or isomerization catalysts such as morpholine, dibutylamine, diethylamine, diethanolamine, thiols and the like. In another improved process for the preparation of these graft polymer dispersions, the improvement consists of preparing a polyetherester polyol by the reaction of a polyoxyalkylene ether polyol, a polycarboxylic acid anhydride to form a half acid ester and an alkylene oxide to obtain a product having an acid number of less than 5 mg KOH/gram which cornprises conducting the reaction between the polyoxyalkylene poly-ether polyol and the anhydride and the following reaction with the alkylene oxide in the presence of an effective amount of a catalyst selected from the group consisting of salts and oxides of divalent metals. The polyols having induced unsaturation are hereinafter referred to as ~Imacro-mers." Chain transfer agents may be employed as reaction moderators particularly at temperatu-res below 105C. The s~s polymerization reaction may be carried out at temperatures between 25C and 180C, preferably between 80C and 135C~
The polyol mixture contains less than 0.1 mole o~ unsatura-tion per mole of polyol mixture and ranges from 0.001 to 0.09 mole of unsaturation~
The alkylene oxides which may be employed for ~he preparation of the polyetherester polyols include ethylene oxide, propylene oxide, butylene oxide, amylene oxide and mixtures of these oxides~
The graft polymer dispersions of this invention have viscosities less than 10,000 cps at 25C. Preferably they have viscosities ranging from 2000 to 8000 cps at 25C.
Among those chain transfer agents which may be employed are as follows: acetic acid, bromoacetic acid, chloroacetic acid, ethyl dibromoacetate, iodoacetic acid, tribromoacetic acid, ethyl tribromoacetate, trichloroacetic acid, ethyl trichloroacetate, acetone, p-bromophenylaceto-nitrile, p-nitrophenylacetylene, allyl alcohol, 2,4,6-trinitroaniline, p-ethynylanisole, 2,4,6-trinitroanisole, azobenzene, benzaldehyde, p-cyanobenzaldehyde, 2-butyl-benzene, bromobenzene, 1,3,5-trinitrobenzene, benzochrysene, ethyl trinitrobenzoate, benzoin, benzonitrile, benzopyrene, tributylborane, 1,4-butanediol, 3,4-epoxy-2-methyl-1-butene, t-butyl ether, t-butyl isocyanide, l-phenylbutyne, p-cresol, p-bromocumene, dibenzonaphthacene, p-dioxane, pentaphenyl ~,~2S4~5 ethane, ethanol, l,l-diphenylethylene, ethylene glycol, ethyl ether, ~luorene, N,N dimethylformamide, 2-heptene, 2-hexe~e, isobutyraldehyde, diethyl bromomalonate, bromotri-chloromethane, dibromoethane, diiodomethane, naphthalene, 1-naphthol, 2-napthol, methyl oleate, 2,4,4-triphenyl-1-pentene, 4-methyl-2-pentene, 2,6-diisopropylphenol, phenyl etherl phenylphosphine, diethylphosphine, dibutylphosphine, phosphorus trichloride, l,l,l-tribromopropane, dialkyl phthalate, 1,2-propanediol, 3-phosphinopropionitrile, 1-propanol, pyrocatechol, pyrogallol, methyl stearate,tetraethylsilane, triethylsilane, dibromostilbene, a~
bromostyrene, ~-methylstyrenel tetraphenyl succinonitrile,
2,4,6-trinitrotoluene, p-toluidine, N,N-dimethyl-p-tolu-idine, a-cyano-p-tolunitrile, ~,~'-dibromo-p-xylene, 2,6-xylenol, diethyl zinc, dithiodiac~tic acid, ethyl dithiodi-acetic acid, 4,4'-dithio-bisanthranilic acid, benzenethiol, o-ethoxybenzenethiol, 2,2'-dithiobisbenzothiazole, benzyl sulfide, l-dodecanethiol, ethanethiol, l-hexanethiol, 1-napthalenethiol, 2-napthalenethiol, l-octanethiol, 1-heptanethiol, 2-octanethiol, l-tetradecanethiol, ~-toluene-thiol, isopropanol, 2-butanol, carbon tetrabromide and tertiary dodecyl mercaptan.
The chain transfer a~ents employed will depend on the particular monomers or mixtures of monomers employed and the molar ratios of such mixtures. The concentration of the ~ ~r~;~a~t~
chain transfer agent whish i5 employed may range from 0.1 to 10 percent by weight based on the weight of monomer.
Representative polyols essentially free from ethylenic unsaturation which may be employed in combination with the macromers of the invention are well known to those skilled in the art. They are often prepared by the cata-lytic 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;
The chain transfer a~ents employed will depend on the particular monomers or mixtures of monomers employed and the molar ratios of such mixtures. The concentration of the ~ ~r~;~a~t~
chain transfer agent whish i5 employed may range from 0.1 to 10 percent by weight based on the weight of monomer.
Representative polyols essentially free from ethylenic unsaturation which may be employed in combination with the macromers of the invention are well known to those skilled in the art. They are often prepared by the cata-lytic 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 poly-ether 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, equivalent weight of the polyols will vary from 100 to 10,000, preferably from 1000 to 3000.
_g_ Any suitable hydroxy-terminated polyester may be used such 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, a, ~-diethylsuccinic acid, isophthalic acid, tere-phthalic acid, hemimellitic acid, and 1,4-cyclohexanedi-carboxylic acid. Any suitable polyhydric alcohol, including 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, 1,2,6-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 for the preparation of the polyesters. Thus, polyester amides may be obtained by S
condensing an amino alcohol such as ethanolamine with the polycarboxylic acid~ set forth above or they may be made using the same components that make up the hydroxyl containing 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 ~he preparation of the hydroxy-terminated polyesters. Any suitable alkylene oxide 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, for example, the process disclosed by Wurtz in 1859 and Encyclopedia of Chemical Technolo~y, Vol. 79 pp. 257-262, published by Interscience Publishers, Inc. (1951) or in UOS. 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'-~4,4'-hydroxyphenyl)propane and blends thereof having equivalent weights of from 100 to 5000.
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 at least two -SH groups such as 1,2-ethanedithiol, 1,2-propane-dithlol, l,3-propanedithiol, and 1,6-hexanedithiol; alkene thiols such as 2-butene-1,4-dithiol; and alkyne thiols such as 3-hexyne-1,6-dithiol.
Suitable amines which may be condensed with alkylene oxides inclu~e aromatic amines such as aniline, o-chloroaniline, p-aminoaniline, 1,5-diaminonaphthalene, methylene dianiline, 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, tri~sopropanolamine, ethylenediamine, 1,3-diaminopropane, 1,3-diaminobutane, and 1,4-diaminobutane.
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 dis-cussion of these polyols and their method of preparation can be found in U.S. Patents NosO 3,585,185; 3,639,541 and 3,639,542.
~25i;~3S
The unsaturated polyols or macromers which are employed in the present invention may be prepared by the reaction of any conventional polyol such as those described above with an organic compound having both ethylenic unsaturation and a hydroxyl, carboxyl, anhydride, isocyanate or epoxy group or they may be prepared by employing an organic compound having both ethylenic unsaturation and a hydroxyl, carboxyl, anhydride, or epoxy group as a reactant in the preparation of the conventional polyol~ Representa-tive of such organic compounds include unsaturated mono- and polycarboxylic acids and anhydrides such as maleic acid and anhydride, fumaric acid, crotonic acid and anhydride, propenyl succinic anhydride, acrylic acid, acryoyl chloride, hydroxy ethyl acrylate or methacrylate and halogena~ed maleic acids and anhydrides, unsaturated polyhydric alcohols such as 2-butene-1,4-diol, glycerol allyl ether, trimethyl-olpropane allyl ether~ pentaerythritol allyl ether, penta-erythritol vinyl ether, pentaerythritol diallyl ether, and l-butene-3,4-diol, unsaturated epoxides such as l-vinyl-cyclohexene-3,4-epoxide, butadiene monoxide, vinyl glycidyl ether(l-vinyloxy-2,3-epoxy propane), glycidyl methacrylate and 3-allyloxypropylene oxide (allyl glycidyl ether). If a polycarboxylic acid or anhydride is employed to incorporate unsaturation into the polyols, it is preferable to react the unsaturated polyol with an alkylene oxide, preferably '~2,ZS48S
ethylene or propylene oxide, to replaee the earboxyl groups with hydroxyl groupæ prior to employment in the present invention. The amount of alkylene oxide employed is such as to reduee the aeid number of the unsaturated polyol to about 5 or less.
The maleated maeromers are isomerized at tempera-tures ranging from 80C to 120C for one-half hour to three hours in the presence of an effeetive amount of an isomeri-zation eatalyst. The catalyst is employed at eoncentrations greater than 0~01 weight percent based on the weight of the maeromer.
When preparing the polyetherester polyol employing the eatalyst seleeted from the group eonsisting of salts and oxides of divalent metals, the coneentration of catalyst which may be employed ranges from 0.005 to 0.5 weight percent based on the weight of polyol mixture. The tempera-tures employed range from 75C to 175C. The equivalent weight of the macromer may vary from 1000 to 10,000, preferably from 2000 to 60000 Among the divalent metals which may be employed are: zine acetate, zinc chloride, zinc oxide, zinc neodec-anoate, tin chloride, calcium naphthenate, ealcium ehloride, ealeium oxide, calcium acetate, copper naphthenate, cadmium acetate, cadmium chloride, nickel chloride, manganese chloride, and manganese acetate.
~5~S
Certain of the above-mentioned catalysts such as - calcium naphthenate promote the isomerization of the maleate to the fumarate structure during the preparation of the macromer, while othars such as zinc chloride, which is an effective catalyst for the polymerization, inhibit this isomerization.
As mentioned above, the graft polymer dispersions of the invention are prepared by the in situ polymerization, in the above-described polyols of an ethylenically un-10 saturated monomer or a mixture of ethylenically unsaturatedmonomers. Representative ethylenically unsaturated monomers which may be employed in the present invention include butadiene, isoprene, 1,4-pentadiene, 1,6-hexadiene, 1,7-octadiene, styrene, -methylstyrene, 2-methylstyrene, 3-methylstyrene and 4-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene, cyclohexylstyrene, benzylstyrene, and the like; substituted styrenes such as cyanostyrene, nitrostyrene, N,N-dimethyl-aminostyrene, acetoxystyrene, methyl 4-vinylbenzoate, phenoxystyrene, p~vinylphenyl oxide, and the like; the acrylic and substituted acrylic monomers such as acrylo-nitrile, acrylic acid, methacrylic acid, methyl acrylate, 2-hydroxyethyl acrylate, methyl methacrylate, cyclohexyl
_g_ Any suitable hydroxy-terminated polyester may be used such 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, a, ~-diethylsuccinic acid, isophthalic acid, tere-phthalic acid, hemimellitic acid, and 1,4-cyclohexanedi-carboxylic acid. Any suitable polyhydric alcohol, including 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, 1,2,6-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 for the preparation of the polyesters. Thus, polyester amides may be obtained by S
condensing an amino alcohol such as ethanolamine with the polycarboxylic acid~ set forth above or they may be made using the same components that make up the hydroxyl containing 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 ~he preparation of the hydroxy-terminated polyesters. Any suitable alkylene oxide 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, for example, the process disclosed by Wurtz in 1859 and Encyclopedia of Chemical Technolo~y, Vol. 79 pp. 257-262, published by Interscience Publishers, Inc. (1951) or in UOS. 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'-~4,4'-hydroxyphenyl)propane and blends thereof having equivalent weights of from 100 to 5000.
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 at least two -SH groups such as 1,2-ethanedithiol, 1,2-propane-dithlol, l,3-propanedithiol, and 1,6-hexanedithiol; alkene thiols such as 2-butene-1,4-dithiol; and alkyne thiols such as 3-hexyne-1,6-dithiol.
Suitable amines which may be condensed with alkylene oxides inclu~e aromatic amines such as aniline, o-chloroaniline, p-aminoaniline, 1,5-diaminonaphthalene, methylene dianiline, 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, tri~sopropanolamine, ethylenediamine, 1,3-diaminopropane, 1,3-diaminobutane, and 1,4-diaminobutane.
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 dis-cussion of these polyols and their method of preparation can be found in U.S. Patents NosO 3,585,185; 3,639,541 and 3,639,542.
~25i;~3S
The unsaturated polyols or macromers which are employed in the present invention may be prepared by the reaction of any conventional polyol such as those described above with an organic compound having both ethylenic unsaturation and a hydroxyl, carboxyl, anhydride, isocyanate or epoxy group or they may be prepared by employing an organic compound having both ethylenic unsaturation and a hydroxyl, carboxyl, anhydride, or epoxy group as a reactant in the preparation of the conventional polyol~ Representa-tive of such organic compounds include unsaturated mono- and polycarboxylic acids and anhydrides such as maleic acid and anhydride, fumaric acid, crotonic acid and anhydride, propenyl succinic anhydride, acrylic acid, acryoyl chloride, hydroxy ethyl acrylate or methacrylate and halogena~ed maleic acids and anhydrides, unsaturated polyhydric alcohols such as 2-butene-1,4-diol, glycerol allyl ether, trimethyl-olpropane allyl ether~ pentaerythritol allyl ether, penta-erythritol vinyl ether, pentaerythritol diallyl ether, and l-butene-3,4-diol, unsaturated epoxides such as l-vinyl-cyclohexene-3,4-epoxide, butadiene monoxide, vinyl glycidyl ether(l-vinyloxy-2,3-epoxy propane), glycidyl methacrylate and 3-allyloxypropylene oxide (allyl glycidyl ether). If a polycarboxylic acid or anhydride is employed to incorporate unsaturation into the polyols, it is preferable to react the unsaturated polyol with an alkylene oxide, preferably '~2,ZS48S
ethylene or propylene oxide, to replaee the earboxyl groups with hydroxyl groupæ prior to employment in the present invention. The amount of alkylene oxide employed is such as to reduee the aeid number of the unsaturated polyol to about 5 or less.
The maleated maeromers are isomerized at tempera-tures ranging from 80C to 120C for one-half hour to three hours in the presence of an effeetive amount of an isomeri-zation eatalyst. The catalyst is employed at eoncentrations greater than 0~01 weight percent based on the weight of the maeromer.
When preparing the polyetherester polyol employing the eatalyst seleeted from the group eonsisting of salts and oxides of divalent metals, the coneentration of catalyst which may be employed ranges from 0.005 to 0.5 weight percent based on the weight of polyol mixture. The tempera-tures employed range from 75C to 175C. The equivalent weight of the macromer may vary from 1000 to 10,000, preferably from 2000 to 60000 Among the divalent metals which may be employed are: zine acetate, zinc chloride, zinc oxide, zinc neodec-anoate, tin chloride, calcium naphthenate, ealcium ehloride, ealeium oxide, calcium acetate, copper naphthenate, cadmium acetate, cadmium chloride, nickel chloride, manganese chloride, and manganese acetate.
~5~S
Certain of the above-mentioned catalysts such as - calcium naphthenate promote the isomerization of the maleate to the fumarate structure during the preparation of the macromer, while othars such as zinc chloride, which is an effective catalyst for the polymerization, inhibit this isomerization.
As mentioned above, the graft polymer dispersions of the invention are prepared by the in situ polymerization, in the above-described polyols of an ethylenically un-10 saturated monomer or a mixture of ethylenically unsaturatedmonomers. Representative ethylenically unsaturated monomers which may be employed in the present invention include butadiene, isoprene, 1,4-pentadiene, 1,6-hexadiene, 1,7-octadiene, styrene, -methylstyrene, 2-methylstyrene, 3-methylstyrene and 4-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene, cyclohexylstyrene, benzylstyrene, and the like; substituted styrenes such as cyanostyrene, nitrostyrene, N,N-dimethyl-aminostyrene, acetoxystyrene, methyl 4-vinylbenzoate, phenoxystyrene, p~vinylphenyl oxide, and the like; the acrylic and substituted acrylic monomers such as acrylo-nitrile, acrylic acid, methacrylic acid, methyl acrylate, 2-hydroxyethyl acrylate, methyl methacrylate, cyclohexyl
4~S
me~hacrylate, benzyl methacrylate, isopropyl methacrylate, octyl methacrylate, methacrylonitrile, ethyl ~-ethoxy-acrylate, methyl ~-acetaminoacrtylate, butyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, phenyl methacrylate, N,N-dimethylacrylamide, N,N-dibenzylacrylamide, N-butyl-acrylamide, methacrylyl formamide, and the like; the vinyl esters, vinyl ethers, vinyl ketones, etc., such as vinyl acetate, vinyl butyrate, isopropenyl acetate, vinyl formate, vinyl acrylate, vinyl methacrylate, vinyl methoxyacetate, vinyl benzoate, vinyltoluene, vinylnaphthalene, vinyl methyl ether, vinyl ethyl ether, vinyl propyl ethers, vinyl butyl . ethers, vinyl 2-ethylhexyl ether, vinyl phenyl ether, vinyl 2-methoxyethyl ether, methoxybutadiene, vinyl 2-butoxyethyl ether, 3,4-dihydro-1,2-pyran, 2-butoxy-2'-vinyloxy diethyl ether, vinyl methyl ketone, vinyl ethyl ketone, vinyl - phosphonates such as vinyl phenyl ketone, vinyl ethyl sulfone, N-methyl-N-vinyl acetamide, N-vinyl-pyrrolidone, vinyl imidazole, divinyl sulfoxide, divinyl sulfone, sodium vinylsulfonate, methyl vinylsulfonate, N-vinyl pyrrole,and the like; dimethyl fumarate, dimethyl maleate, maleic acid, crotonic acid, fumaric acid, itaconic acid, monomethyl itaconate, t-butylaminoethyl methacrylate, dimethylamino ethyl methacrylate, glycidyl acrylate, allyl alcohol, glycol monoesters of itaconic acid, vinyl pyridine, and the like.
Any of the known polymerizable monomers can be used and the ~L2ZS~LlY5i compounds listed above are illustrative and not restrictive of the monomers suitable for use in this invention.
Preferably, the monomer is selected from the group con-sisting of acrylonitrile, styrene and mixtures thereofO
The amount of ethylenically unsaturated monomer employed in the polymerization reaction i5 generally from 25 percent to 60 percent, preferably from 30 percent to 45 percent, based on the total weight of the product. The polymerization occurs at a temperature between about 25C
and 180C, preferably from 80C to 135C. It is preferred that at least 55 to 100 weight percent of the mGnomer employed i5 styrene or 4-methylstyrene.
Illustrative polymerization initiators which may be employed are the well-known free radical types of vinyl polymerization initiators such as the peroxides, per-sulfates, perborates, percarbonates, azo compounds, etc These include hydrogen peroxide, dibenzoyl peroxide, acetyl peroxide, benzoyl hydroperoxide, t-butyl hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, butyryl peroxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, paramenthane hydroperoxide, diacetyl peroxide, di-l-cumyl peroxide, dipropyl peroxide,diisopropyl peroxide, isopropyl-t-butyl peroxide, butyl-t-butyl peroxide, difuroyl peroxide, bis(triphenylmethyl) peroxide, bis(p-methoxybenzoyl) peroxide, p-monomethoxybenzoyl peroxide, rubene peroxide,
me~hacrylate, benzyl methacrylate, isopropyl methacrylate, octyl methacrylate, methacrylonitrile, ethyl ~-ethoxy-acrylate, methyl ~-acetaminoacrtylate, butyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, phenyl methacrylate, N,N-dimethylacrylamide, N,N-dibenzylacrylamide, N-butyl-acrylamide, methacrylyl formamide, and the like; the vinyl esters, vinyl ethers, vinyl ketones, etc., such as vinyl acetate, vinyl butyrate, isopropenyl acetate, vinyl formate, vinyl acrylate, vinyl methacrylate, vinyl methoxyacetate, vinyl benzoate, vinyltoluene, vinylnaphthalene, vinyl methyl ether, vinyl ethyl ether, vinyl propyl ethers, vinyl butyl . ethers, vinyl 2-ethylhexyl ether, vinyl phenyl ether, vinyl 2-methoxyethyl ether, methoxybutadiene, vinyl 2-butoxyethyl ether, 3,4-dihydro-1,2-pyran, 2-butoxy-2'-vinyloxy diethyl ether, vinyl methyl ketone, vinyl ethyl ketone, vinyl - phosphonates such as vinyl phenyl ketone, vinyl ethyl sulfone, N-methyl-N-vinyl acetamide, N-vinyl-pyrrolidone, vinyl imidazole, divinyl sulfoxide, divinyl sulfone, sodium vinylsulfonate, methyl vinylsulfonate, N-vinyl pyrrole,and the like; dimethyl fumarate, dimethyl maleate, maleic acid, crotonic acid, fumaric acid, itaconic acid, monomethyl itaconate, t-butylaminoethyl methacrylate, dimethylamino ethyl methacrylate, glycidyl acrylate, allyl alcohol, glycol monoesters of itaconic acid, vinyl pyridine, and the like.
Any of the known polymerizable monomers can be used and the ~L2ZS~LlY5i compounds listed above are illustrative and not restrictive of the monomers suitable for use in this invention.
Preferably, the monomer is selected from the group con-sisting of acrylonitrile, styrene and mixtures thereofO
The amount of ethylenically unsaturated monomer employed in the polymerization reaction i5 generally from 25 percent to 60 percent, preferably from 30 percent to 45 percent, based on the total weight of the product. The polymerization occurs at a temperature between about 25C
and 180C, preferably from 80C to 135C. It is preferred that at least 55 to 100 weight percent of the mGnomer employed i5 styrene or 4-methylstyrene.
Illustrative polymerization initiators which may be employed are the well-known free radical types of vinyl polymerization initiators such as the peroxides, per-sulfates, perborates, percarbonates, azo compounds, etc These include hydrogen peroxide, dibenzoyl peroxide, acetyl peroxide, benzoyl hydroperoxide, t-butyl hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, butyryl peroxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, paramenthane hydroperoxide, diacetyl peroxide, di-l-cumyl peroxide, dipropyl peroxide,diisopropyl peroxide, isopropyl-t-butyl peroxide, butyl-t-butyl peroxide, difuroyl peroxide, bis(triphenylmethyl) peroxide, bis(p-methoxybenzoyl) peroxide, p-monomethoxybenzoyl peroxide, rubene peroxide,
5~L8 5;
ascaridol, t-butyl peroxybenzoate, diethyl peroxyterephtha-late, propyl hydroperoxide~ isopropyl hydroperoxide, n-butyl hydroperoxide, t-butyl hydroperoxide, cyclohexyl hydroper-oxide, trans-decalin hydroperoxide, ~-methylbenzyl hydroper-oxide, ~-methyl-~-ethyl benzyl hydroperoxide, tetralin hydroperoxide, ~riphenylmethyl hydroperoxide, diphenylmethyl hydroperoxide, ,~'-azobis-(2-methyl heptonitrile~, 1,1'--azo-bis(cyclohexane carbonitrile), 4,4'-azobis(4-cyanopen-tanoic acicl), 2,2'-azobis(isobutyronitrile), l-t-butylazo-l-cyanocyclohexane, persuccinic acid, diisopropyl peroxy dicarbonate, 2,2'-azobis(2,4-dimethylvaleronitrile), 2-t-butylazo-2-cyano-4-methoxy-4-methylpentane,2,2'-azobis-2-methylbutanenitrile, 2-t-butylazo-2-cyanobutane, l-t-amylazo-l-cyanocyclohexane, 2,2'-azobis~2,4-dimethyl-4-methoxyvaleronitrile, 2,2'-azobis-2-methyl-butyronitrile, 2-t-butylazo-2-cyano-4-methylpentane, 2-t-butylazo-2-iso-butyronitrile, to butylperoxyisopropyl carbonate and the like; a mixture of initiators may also be used. The preferred initiators are 2,21-azobis(2-methylbutyronitrile), 2,2'-azobis(isobutyronikrile), 2,2'-azobis(2~4-dimethyl-valeronitrile), 2-t-butylazo-2-cyano-4-methoxy-4-methyl pentane, 2-t-butylazo-2-cyano-4-methylpentane, 2-t-butylaæo-2-cyano-butane and lauroyl peroxide. Generally, from about 0.1 percent to about 10 percent, preferably from about 1 percent to about 4 percent, by weight of initator based on S~5 the weight of the monomer will be employed in the process of the invention.
The polyurethane foams employed in the present invention are generally prepared by the reaction of a graft polymer dispersion with an organic polyisocyanate in the presence of a blowing agent and optionally in the presence of additional polyhydroxyl-containing components, chain-extending agents, catalysts~ surface-active agents, stabil-izers, dyes, fillers and pigments. Suitable processes for the preparation of cellular polyurethane plastics are disclosed in U.S, Reissue Patent 24,514 together with sui~able machinery to be used in con~unction therewith.
When water is added as the blowing agent, corresponding quantities of excess isocyanate to react with the water and produce carbon dioxide may be used It is possible to proceed with the preparation of the polyurethane plastics by a prepolymer technique wherein an excess of organic polyiso-cyanate is reacted in a first 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'l technique of preparing polyurethanes Furthermore, instead of water, low boiling hydrocarbons such as pentane, hexane, heptane, ~ 2 ~L~ 5 pentene, and heptene; azo compounds such as azohexahydro-benzodinitrile; halogenated hydrocarbons such as dichlorodi-fluoromethane, trichlorofluoromethane, dichlorodi~luoro~
ethane, vinylidene chloride, and methylene chloride 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 of 2,40 and 2,6-toluene diisocyanate, hexamethylene diisocyanate, ~etramethylene diisocyanate, cyclohexane-1,4-diisocyanate, hexahydrotoluene diisocyanate (and isomers), naphthalene-l,S-diisocyanate, l-methoxyphenyl-2,4-diiso-cyanate, 4,4' diphenylmethane diisocyanate, 4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, ~3'-~imethyl-4,4'-biphenyl diisocyanate and 3,3'-dimethyl-diphenylmethane-4,4'-diisocyanate; the triisocyanates such 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 poly-phenylene polyisocyanate. Especially useful due to their availabillty and properties are toluene diisocyanate, 4,4'-diphenylmethane diisvcyanate and polymethylene polyphenylene polyisocyanate.
~2S~S
Crude polyisocyanates may also be used in the composition~ 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.SO Patent No. 3,215,652.
As men~ioned above, the graft polyols may be employed along with another polyhydroxyl-containing compo-nent commonly employed in the art. Any of the polyhydroxyl-containing components which are described above for use in the preparation of the graft polyols may be employed in the preparation of the polyurethane foams useful in ~he present invention.
Chain-extending agents which may be employed in the preparation of the polyurethane foams include those compounds having at least 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 diamines which react more readily with the prepolymer than does wa~er such as phenylene diamine, 1,4-cyclohexane-bis-(methylamine), ethylenediamine, diethylenetriamine, N-(2-hydroxypropyl)-~2~4~3~S
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, ~l-cocomorpholine, l-me~hyl-4-dime~hylaminoethylpiperazine, 3-methoxypropyldimethylamine, N,N,N'-trimethylisopropyl propylenediamine, 3-diethylaminopropyldiethylamine, dio methylbenzylamine, and the like. Other suitable catalysts are, for example, stannous chlorideldibutyltin 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 according 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 ~urface 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 alkyl acid sulfate esters, alkyl sulfonic esters, and alkyl arylsulfonic acid~.
~2S'~
It has been ound in the preparation ~f the flame retardant polyurethane foam products which have incorporated therein the graf~ polymer disper~ions of the invention that less flame retardant compound is necessary to impart flame retardency. Among the flame retardants which may be employed are: pentabromodiphenyl oxidP, dibromopropanol, tris(~-chloropropyl)phosphate, 2,2-bis(bromoethyl) 19 3-propanediol, tetrakis(2-chloroethyl)ethylene diphosphate~
tris(2,3-dibromopropyl~phosphate, tris(~-chloroethyl~-phoshate, tris(l,2-dichloropropyl)phosphate, bis-~2-chloro-ethyl) 2-chloroethylphosphonate, molybdenum trioxide, ammonium molybdate, ammonium phosphate, pentabromodiphenyl-oxide, tricresyl phosphate 9 hexabromocyclodoa~cane and dibromoethyl- dibromocyclohexane. The concentrations of flame retardant compounds which may be employed range from 5 to 25 parts per 100 parts of polyol mixture.
The following examples illustrate the nature of the invention. A11 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 s Compression Set - D395 Compression Load - D1564 Humid Aging - D1564 The following abbreviations are employed in the exampl~s below:
Polyol A is a trimethylolpropane, propylene oxide, ethylene oxide adduct containing 15 percent ethylene oxide, and a hydroxyl number of 25.
Polyol B is a glycerine, propylene oxide, ethylene 02ide adduct containing 12.5 percent ethylene oxide, and a hydroxyl number of 500 Polyol C is a glycerine, propylene oxide, ethylene oxide adduct containing 18.5 percent ethylene oxide, having a hydroxyl number of 35.
Polyol ~ is Polyol A containing 0.5 mole of unsaturation per mole of polyol.
Polyol E is Polyol A containing 0.7 mole of unsaturation per mole of polyol.
Polyol F is a glycerine, ethylene oxide, propylene oxide adduct containing 6 percent ethylene oxide having a reduced unsaturation of 0.3 mole per mole of polyol, containing 36 weight percent of 3:1 acrylonitrile:styrene based on the total weight of ~he polymer and having a hydroxyl number of 32.5.
Polyol G see procedure D.
~254~5 Polyol H is a glycerine~ ethylene oxide propylene oxide adduct containing 16.~ percent ethylene oxide and having a hydroxyl number oE 35.
Polyol I see procedure E~
Polyol J see procedure B.
~atalyst A - zinc neodeconate as ppm zinc.
Catalyst B - calcium naphthenate as ppm calcium.
Catalyst C - copper naphthena~e as ppm copper.
Ca~alyst D - cobalt naphthenate aæ ppm cobalt Initiator A - 2,2'-azobisl2-methylbutyronitrile) DE-71 is pentabromodiphenyl oxide manufactured by Great Lakes Chemicals~
Thermolin*101 is tetrakis(2-chloroethyl)ethylene diphos-phate .
Reactant Blue X-44 is a dye manufacture by Milliken, Inc~
L-5720 is a silicone surfactant manufactured by Union Carbon and Carbide Corporation.
DABCO*TL is an amine cataly~t manufactured by Air Products, Inc.
T 10 is an organo tin catalyst manufactured by M~T
Chemicals, Inc.
DOP is dioctylphthalate.
TDI is toluene diisocyanate.
* Trademark ~2~Z59L~35 .
L-5043 is a silicone surfactant manufactured by Dow Corning Corporation.
T-12 i dibutyltin ~ilaurate DABCO*33LV is a 33 percent ~olution of triethylene diamine in 67 percent dipropylene glycol.
NIAX*A-l is an amine eatalyst manufactured by Union Carbon and Carbide Corporation.
AN is acrylonitrile Sty is styrene Antiblaze 19 repu~edly has the structure ( CE~ 3-- ) xP~ ~ OCH 2--C ~ ,, P--CH 3 ) 2--X
wherein x i~ equal to 0 or 1.
Procedure A
Charses:
The following ~harges were employed in examples 1 through 17 ex~ept as noted otherwise in Table I.
2000 gm Polyol A
30.6 gm maleic anhydride (0.8 equivalents per mole of Polyol A) gm catalyst B 200 ppm calcium 96 gm ethylene oxide (0~01 percent maximum water ) * Trademark -27-~;$
~z~s A 3-liter round-bot~om flask with a stirrer, thermometer and gas inlet was charged with polyol A, maleic anhydride and calcium naphthenata. The contents were heated to 125C and allowed to react for 1 hour. This intermediate was transferred to a l-ga~llon steam heated stainless steel autoclave. After heating to 125C and pressurizing the reactor to 34 psig with nitrogen, ethylene oxide was added during 1 hour and the mixture was reacted for 8 hours. The product was isolated after discharging by stripping the 10volatiles at 105C for 1 hour at <10 mm ~g. This product is designated as polyol D.
Procedure B
Charges: To reactor: 50 g polyol D
925 g polyol B
2.0 g initiator A
Stream #1: 260 g acrylonitrile 790 g styrene 13.5 g l-dodecanethiol Stream #2: 975 g polyol B
20 10.5 g initator A
Reaction Conditions: reaction temperature, 90C; monomer addition time, 210 minutes; polyol initiator addition time, 220 minutes; reaction time, 30 minutes; 300 rpm stirring.
The reactor charges were added to a 5-liter 4-neck flask fitted with a stirrer, nitrogen inlet, addition tube, water condenser and thermowell. After heating the polyol reaction mixture to 90C and holding for 30 minutes under nitrogen, the streams #l and $2 were added through a Kenics static mixer over the specified time period. Upon comple-tion of stream #l addition, the reaction mixture was heated to 110C and reacted for the specified time. After the reaction period was completed, the reaction mixture was vacuum stripped for 30 minutes at 115C and 1 mm Hg. The polyol from this procedure is designated as polyol J.
Procedure C
Charges: 400 lbs. polyol A
7.72 lbs. maleic anhydride 17.24 lbs. ethylene oxide The indicated amount of polyol A was charged to a clean, dry, nitrogen purged 90-gallon reactor, sealed and heated to 110C. The polyol was then flash stripped at less than 10 mm Hg into a cleanr dry 60-gallon reactor. Strip-ping was continued until the residual water level had beenreduced to 0.01 weight percent. After stripping was completed, maleic anhydride was added to the polyol, the reaction mixture was padded with 34 psi nitrogen and then :~fZZ~S
heated to 150C. AEter reacting for 4 hours, excess ethylene oxide was added over 5 hours at 150C. This reaction mixture was allowed to react 8 to 12 hours or until the acid number had dropped below 0.2 mg KOH/g. The mixture was then stripped to remove excess ethylene oxide. This product was designated as polyol E.
Procedure D
Charges: To reac~or: 10.67 lbs~ polyol E
93.33 lbs. polyol B
0.053 lb. morpholine 0.21 lb. initiator A
Stream #1: 28.0 lbs. acrylonitrile 84.0 lbs. styrene 1.12 lbs~ l-dodecanethiol Stream #2: 104.0 lbs. polyol B
1,12 lbs. initiator A
Reaction Conditions: reaction temperature, 90C; monomer addition time, 210 minutes; polyol-initiator addition time, 220 minutes; reaction time, 30 minutes.
The reactor ch~rges were added under a nitrogen atomsphere to a 50-gallon reactor. After heating the polyol reaction mixture to 90C and holding for 30 minutes, streams #1 and #2 were added through a Kenics static mixer over the specified time period. Upon completion of stream #l addition, the reaction mixture was heated to 110C and 12~ S
reacted for the specified time. After the reaction period was completed, -the reaction mixture was vacuum stripped for 3 hours at 125C and 5 mm Hg. This product is designated as polyol G.
Procedure E
Charges: To reactor~ 85.3 lbs. polyol C
26.7 lbs. polyol A
0.19 lb. initiator A
Stream #1: 24 lbs. acrylonitrile 72 lbs. styrene 0.96 lb. l-dodecanethiol Stream ~2: 112.0 lbs. polyol C
0.96 lb. initator A
Reaction Conditions: reaction temperature, 90C; monomer addition time, 180 minutes; polyol-initiator addition time, 190 minutes; reaction tim~, 30 minutes.
. The same reaction procedure was used here as in procedure D.
This product is designated polyol I.
~s~
Examples 1-17 The products of these exam~les were prepared employing various catalystsl at various concentrations and at variable maleic anhydride contents using procedure A.
~2~59~5 .~U o o o o In o o u~ O c~ o o o o o o o O O ~ O CO l~ CJ~ ~ ~ ~ ~ ~ ~`
u~ ~ o~ ~ ~ ~ o ~r ~ ~ o o~ ~ ~ el~ O O
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.~
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ooooooooooooooooo c~a~
a ~i~: m u ~ a: m m m m m m m m m m m m '' ~ ~' u~
~g ooooo_i_ioooooooooo O,~
a) g o Examples 18-41 The products listed in Table II and III were prepared by procedure B emplo~ing the indicated polyols, monomers and concentrations.
~2Z5~35 o o o o ~ o o o o o o o o o o o o o U~ ~ el' r~ t` ~ ,1 ~ U~ U~ O er 0~ ~ ~9 1 O ~
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r~l L
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Examples 42-93 Examples 48 and 52 were prepared by adding to a 500 ml flask fitted with a stirrer and a nitrogen inlet tube, 700 grams of polyol E and 0.7 grams of morpholine.
The reaction mixture was heated to 90C for 1 hour, then vacuum stripped for 30 minutes at 1 mm Hg pressure.
Analysis by nuclear magnetic resonance showed 0.85 moles of fumarate unsaturation. This product was used in preparing the products of Examples 48 and 52. The remainder of the examples were prepared employing procedure D.
S4~S
m ~ ~ ~ 2 " ~ o 8 ~ ~ 1~ ~ o~ ~ o ~ ~ ~ ~`
~ ~
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i~ ~ ,_1 c~l ~ ~ O o u~ u~ u~ U~ ~ u7 ~ ~ In ul m ~ Ln O U ~ o g n pl ~ OD ~0 --I ~1 ~ r t r~l r~
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111 L'~ L't L'l L'~
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~5~
Examples_94-110 The products of Table V were prepared employing procedure E except products of Examples 111 and 112 where polyol E was replaced by polyol A.
-~2-~t.
o ~ o o o o o o C~ o ~ o o o o o o o ~ ~Oæ ~
U1 o ~ o O o O o In O O O O C~ O O O
~5 ~ o o o u~
m ~ ~ ~ ~ ~ ~ _~ ~ ~ ~ ~ ,~ ~ ~ ~ ~ ~ ~
o u~ o o o Is~
o~ oOo~ooooooooooooo rn ~ Ln ~ o - I ~ ~) ~ In ~ I~ oo a~ o ~ c~ ~o o ~ o o ~o ~ ~ ~ ~ ~
~.22~ 5 Examples 111-127 The polyurethane foams of Tables VI, VII and VIII
were prepared by charging a cne 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.
Tables VI, VII and VIII set 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 California No. 117 open flame test, indicate that flame retardancy may be obtained with reasonably low levels of flame retardant compounds employin~ the polymer dispersions of the instant invention.
12'254BS
TABIE VI
EKample 111 112 113 114 115 116 Polyol G G G F F F
E~rnulation, p~w Polyol 100.0 q~lE~LIN~01 3, 0 6.0 12.0 3.0 6.0 12.0 RE~r ~lue X-44 0~25 GoS 1~0 0~25 0~5 1~0 ~ater 2. 8 -- --1 0 ~*TL O . 11 T-10 û. 4~
D~P 0.~ ____ TDI 37.1~------Foam Pro~erties Den~ity, pcf ~.18 2.25 2.24 2.17 2.19 2.33 Tensile strength, psi 23.3 25.8 25.6 28.1 2~.4 27.8 Elon~ation, % 77 87 110 73 90 93 Tear, pi 20~ 2.3 3.1 2.0 201 2.5 2 0 P~silienoe, % 30 26 28 32 24 26 ILD, lb/~0 sq.in. (4 inch) 2s% 118.0112.0 10~.0 124.0 116.4 110.0 65% 247.2231.6 211.6 264.0 242.0 232.4 25~6 retllrn 69.2 67.2 57.2 68.8 64.4 62.8 Sag factor 2.09 2.07 2.07 2.13 2.08 2.11 Guide factor 54.1 49.8 45.5 57.1 53.2 47.2 ~very, % 5~.0 60.0 ~6.0 55.0 55.0 57.~
50~ 57.1 71.3 89.7 14.5 58~2 72.0 9096 81.1 95.7 9~1.0 83.4 95.8 96.8 30 ~nid aged 5 hrs. at ~50F
CLD, % of ori~3inal 5096 61.1 71.0 7~.0 80.0 84.0 79.0 ~npression sets, %
50P6 57.4 66.9 87.0 25.4 57.7 66.1 90~ 76.3 92.9 97.6 26.2 83.8 ~0.2 Heat aged 22 hrs.
at 284~F tensile strength ,psi 29. 631. 8 31. 6 31. 5 33. 034 . 9 Air flowi c~n 3.80 0086 0.~5 1.92 1.10 1.10 Foam ~olor white tan *Trade mark ~`. ' '~
.:J
~Z'~5 ~r~sLE VI - continued Exa~le 117118 119 120 121 122 Polyol G G G F F F
Water 2. 8~
DE-71 6~0------------- ~~~ - ~ ~~~~~~ -~ERMOLIN 101 3.0 600 12.0 3.0 600 12.0 CALIFOKNIA NO. 117 SECTION A PART I -- OPEN FI~ME TEST
.
Spec.
Original Max.
Afterflame, sec.
10average 5.0 18~6 2.6 2.630.034.037nO
maximum 10.0 22~0 4~0 3~032~035~038.0 Char length, in.
average 6.0 5~4 2~6 2~612.012.012.0 maxim~n 8.0 6.0 3~3 20912.0120012.0 Heat aged 24 hrs./220F
Afterflame, sec.
average 5.0 16.8 3.4 3.232.035~038~0 maximum 10.0 20~0 4~0 4~032~035~03~0 Char length, in.
20average 600 5~3 2~7 2~612~012~012~0 maximum 8.0 5.9 3.0 3.012~012~012~0 CALIFORNIA NO~ 117 SECTION D PART~ II -- S~LDERING SCREENING TEST
.
Spec.
Min.
Non smoldered residue, % 80.0 93.8 97.3 97.7 bumed co~pletely BurL~ CHI~EY
~eight retention,96 69.1 92.7 95~5 0 63~0 941~5 Flame height,cm 25+ 22 19 25+ 25+ 20+
DOC FF-1--70MENqHE~sMINE PILL ~ME TEST
Spec.
3 o Min.
Inches bun.ed fromouter ring >1 2.93~4 3~3 2.9 3.2 3.1 OXYGEN INDEX
% 2 19.721.3 24.3 1~.7 20.9 21~5 --46~
TABLE VII
BLENDS OF POLYOL I/ POLYOL H
Example 123 124 Formulation .
Eblyol I 30 30 Pblyol H 70 70 Water 2.0 2.0 DEOA 0.8 0.8 L 5043 0.8 0.8 TffERMOLIN 101 3.0 3.0 T-12 0.06 0.06 ~BCO 33L~l 0.18 0.18 NIAX A-l 0.06 0.06 TDI index 108 108 California No. 117 Section A Part I - Open Flame Tbst Sp~c.
Max.
Afterflame, sec.
average 0.7 0.7 5.0 maximum 0.8 0.8 10.0 Char length, in.
average 2.1 2.3 6.0 maximum 2.2 2.5 8.0 California No. 117 Section D Part II - Smoldering & reening Test Spec.
Min.
Non-smoldered residue, % 86.4 89.0 80 ~,2259L~5;
TABI~ VIII
Ex~mple 125 126 127 Formulation Polyol J 100.0~
'lff~RMOLIN 101 3.0 12.0 --DE~71 -- -- 12.0 ANTIBL~ZE 19 ~ -- 5.0 Silicone Lr5720 1.0--- ~---~---- ----------Water 2.4-- -- -- -~ - ~-~ --DABCO TL 0.1-- - ---- - - -------~
T'10 0.4 0.4 3 DOP 0.8 0.8 Q.6 TDI (115 index) 32.5--- -Foam Properties Density, pcf 2.19 2,32 2.27 Tensile strength, psi 24.6 26.2 25.3 Elongation, % 70 127 100 Tear, pi 2.5 2.9 2.5 Resilience, % 26 30 32 ILD, lb/50 sq.in. (4 inch) 25% 119.2 119.6 97.0 266.4 244.4 23~.1 25% retNrn 71.2 72.0 49.2 Sag factor 2.23 2.04 2.45 Guide factor 54.4 51.6 42.7 ~eoovery, % 60.0 60.0 51.0 Compression sets, %
50% 25.4 82.4 73.9 9o% 53.4 96.1 96.2 Humid aged 5 hrs. at 250F
CLD, % of ori~inal 50% 80.0 67.0 82.0 Compression sets, ~
50~ 23.9 65.4 59.5 90~ 27.7 95.6 9205 Heat aged 22 hrs. at 284F
tensile strength, psi 33.5 30.6 30.1 Air flow, cfm 0.53 0.50 0.50 Color white ~,,2S~8S
TABLE VIII - c~on~inued EXample 125 126 127 CALIFORNIA NO. 117 SECTION A PART I - OPEN FLAME TEST
Spec.
Original Max.
AEterflame, sec.
average 5.0 19.4 1.6 1 6 maximum 10.0 26.0 3.0 2.0 Char length, in.
average 6.0 7.8 2.0 2.4 maximum 8.0 9.0 3.1 3.0 ~leat aged 24 hrs./220F
Afterflame, sec.
average 5.0 15.2 1.4 1.2 maximum 10.0 21.0 3.0 2.0 Char length, in.
average 6.0 6.5 2.3 2.8 maximum 8.0 8.7 3.1 3.1 CA~IFORNIA NO. 117 SECTION D PART II - SMDLDERING SCREENING TEST
.
Spec.
Max.
Non-sm~ldered residue, % 80.0 96.6 99.2 99.9 BUTLER CHIMNEY
Weight retention, % 34.6 94.3 92.9 Flame height, cm 25+ 17 14 Spec.
Min.
Inches burned from outer ring >1 3.5 3.3 3.1
ascaridol, t-butyl peroxybenzoate, diethyl peroxyterephtha-late, propyl hydroperoxide~ isopropyl hydroperoxide, n-butyl hydroperoxide, t-butyl hydroperoxide, cyclohexyl hydroper-oxide, trans-decalin hydroperoxide, ~-methylbenzyl hydroper-oxide, ~-methyl-~-ethyl benzyl hydroperoxide, tetralin hydroperoxide, ~riphenylmethyl hydroperoxide, diphenylmethyl hydroperoxide, ,~'-azobis-(2-methyl heptonitrile~, 1,1'--azo-bis(cyclohexane carbonitrile), 4,4'-azobis(4-cyanopen-tanoic acicl), 2,2'-azobis(isobutyronitrile), l-t-butylazo-l-cyanocyclohexane, persuccinic acid, diisopropyl peroxy dicarbonate, 2,2'-azobis(2,4-dimethylvaleronitrile), 2-t-butylazo-2-cyano-4-methoxy-4-methylpentane,2,2'-azobis-2-methylbutanenitrile, 2-t-butylazo-2-cyanobutane, l-t-amylazo-l-cyanocyclohexane, 2,2'-azobis~2,4-dimethyl-4-methoxyvaleronitrile, 2,2'-azobis-2-methyl-butyronitrile, 2-t-butylazo-2-cyano-4-methylpentane, 2-t-butylazo-2-iso-butyronitrile, to butylperoxyisopropyl carbonate and the like; a mixture of initiators may also be used. The preferred initiators are 2,21-azobis(2-methylbutyronitrile), 2,2'-azobis(isobutyronikrile), 2,2'-azobis(2~4-dimethyl-valeronitrile), 2-t-butylazo-2-cyano-4-methoxy-4-methyl pentane, 2-t-butylazo-2-cyano-4-methylpentane, 2-t-butylaæo-2-cyano-butane and lauroyl peroxide. Generally, from about 0.1 percent to about 10 percent, preferably from about 1 percent to about 4 percent, by weight of initator based on S~5 the weight of the monomer will be employed in the process of the invention.
The polyurethane foams employed in the present invention are generally prepared by the reaction of a graft polymer dispersion with an organic polyisocyanate in the presence of a blowing agent and optionally in the presence of additional polyhydroxyl-containing components, chain-extending agents, catalysts~ surface-active agents, stabil-izers, dyes, fillers and pigments. Suitable processes for the preparation of cellular polyurethane plastics are disclosed in U.S, Reissue Patent 24,514 together with sui~able machinery to be used in con~unction therewith.
When water is added as the blowing agent, corresponding quantities of excess isocyanate to react with the water and produce carbon dioxide may be used It is possible to proceed with the preparation of the polyurethane plastics by a prepolymer technique wherein an excess of organic polyiso-cyanate is reacted in a first 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'l technique of preparing polyurethanes Furthermore, instead of water, low boiling hydrocarbons such as pentane, hexane, heptane, ~ 2 ~L~ 5 pentene, and heptene; azo compounds such as azohexahydro-benzodinitrile; halogenated hydrocarbons such as dichlorodi-fluoromethane, trichlorofluoromethane, dichlorodi~luoro~
ethane, vinylidene chloride, and methylene chloride 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 of 2,40 and 2,6-toluene diisocyanate, hexamethylene diisocyanate, ~etramethylene diisocyanate, cyclohexane-1,4-diisocyanate, hexahydrotoluene diisocyanate (and isomers), naphthalene-l,S-diisocyanate, l-methoxyphenyl-2,4-diiso-cyanate, 4,4' diphenylmethane diisocyanate, 4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, ~3'-~imethyl-4,4'-biphenyl diisocyanate and 3,3'-dimethyl-diphenylmethane-4,4'-diisocyanate; the triisocyanates such 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 poly-phenylene polyisocyanate. Especially useful due to their availabillty and properties are toluene diisocyanate, 4,4'-diphenylmethane diisvcyanate and polymethylene polyphenylene polyisocyanate.
~2S~S
Crude polyisocyanates may also be used in the composition~ 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.SO Patent No. 3,215,652.
As men~ioned above, the graft polyols may be employed along with another polyhydroxyl-containing compo-nent commonly employed in the art. Any of the polyhydroxyl-containing components which are described above for use in the preparation of the graft polyols may be employed in the preparation of the polyurethane foams useful in ~he present invention.
Chain-extending agents which may be employed in the preparation of the polyurethane foams include those compounds having at least 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 diamines which react more readily with the prepolymer than does wa~er such as phenylene diamine, 1,4-cyclohexane-bis-(methylamine), ethylenediamine, diethylenetriamine, N-(2-hydroxypropyl)-~2~4~3~S
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, ~l-cocomorpholine, l-me~hyl-4-dime~hylaminoethylpiperazine, 3-methoxypropyldimethylamine, N,N,N'-trimethylisopropyl propylenediamine, 3-diethylaminopropyldiethylamine, dio methylbenzylamine, and the like. Other suitable catalysts are, for example, stannous chlorideldibutyltin 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 according 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 ~urface 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 alkyl acid sulfate esters, alkyl sulfonic esters, and alkyl arylsulfonic acid~.
~2S'~
It has been ound in the preparation ~f the flame retardant polyurethane foam products which have incorporated therein the graf~ polymer disper~ions of the invention that less flame retardant compound is necessary to impart flame retardency. Among the flame retardants which may be employed are: pentabromodiphenyl oxidP, dibromopropanol, tris(~-chloropropyl)phosphate, 2,2-bis(bromoethyl) 19 3-propanediol, tetrakis(2-chloroethyl)ethylene diphosphate~
tris(2,3-dibromopropyl~phosphate, tris(~-chloroethyl~-phoshate, tris(l,2-dichloropropyl)phosphate, bis-~2-chloro-ethyl) 2-chloroethylphosphonate, molybdenum trioxide, ammonium molybdate, ammonium phosphate, pentabromodiphenyl-oxide, tricresyl phosphate 9 hexabromocyclodoa~cane and dibromoethyl- dibromocyclohexane. The concentrations of flame retardant compounds which may be employed range from 5 to 25 parts per 100 parts of polyol mixture.
The following examples illustrate the nature of the invention. A11 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 s Compression Set - D395 Compression Load - D1564 Humid Aging - D1564 The following abbreviations are employed in the exampl~s below:
Polyol A is a trimethylolpropane, propylene oxide, ethylene oxide adduct containing 15 percent ethylene oxide, and a hydroxyl number of 25.
Polyol B is a glycerine, propylene oxide, ethylene 02ide adduct containing 12.5 percent ethylene oxide, and a hydroxyl number of 500 Polyol C is a glycerine, propylene oxide, ethylene oxide adduct containing 18.5 percent ethylene oxide, having a hydroxyl number of 35.
Polyol ~ is Polyol A containing 0.5 mole of unsaturation per mole of polyol.
Polyol E is Polyol A containing 0.7 mole of unsaturation per mole of polyol.
Polyol F is a glycerine, ethylene oxide, propylene oxide adduct containing 6 percent ethylene oxide having a reduced unsaturation of 0.3 mole per mole of polyol, containing 36 weight percent of 3:1 acrylonitrile:styrene based on the total weight of ~he polymer and having a hydroxyl number of 32.5.
Polyol G see procedure D.
~254~5 Polyol H is a glycerine~ ethylene oxide propylene oxide adduct containing 16.~ percent ethylene oxide and having a hydroxyl number oE 35.
Polyol I see procedure E~
Polyol J see procedure B.
~atalyst A - zinc neodeconate as ppm zinc.
Catalyst B - calcium naphthenate as ppm calcium.
Catalyst C - copper naphthena~e as ppm copper.
Ca~alyst D - cobalt naphthenate aæ ppm cobalt Initiator A - 2,2'-azobisl2-methylbutyronitrile) DE-71 is pentabromodiphenyl oxide manufactured by Great Lakes Chemicals~
Thermolin*101 is tetrakis(2-chloroethyl)ethylene diphos-phate .
Reactant Blue X-44 is a dye manufacture by Milliken, Inc~
L-5720 is a silicone surfactant manufactured by Union Carbon and Carbide Corporation.
DABCO*TL is an amine cataly~t manufactured by Air Products, Inc.
T 10 is an organo tin catalyst manufactured by M~T
Chemicals, Inc.
DOP is dioctylphthalate.
TDI is toluene diisocyanate.
* Trademark ~2~Z59L~35 .
L-5043 is a silicone surfactant manufactured by Dow Corning Corporation.
T-12 i dibutyltin ~ilaurate DABCO*33LV is a 33 percent ~olution of triethylene diamine in 67 percent dipropylene glycol.
NIAX*A-l is an amine eatalyst manufactured by Union Carbon and Carbide Corporation.
AN is acrylonitrile Sty is styrene Antiblaze 19 repu~edly has the structure ( CE~ 3-- ) xP~ ~ OCH 2--C ~ ,, P--CH 3 ) 2--X
wherein x i~ equal to 0 or 1.
Procedure A
Charses:
The following ~harges were employed in examples 1 through 17 ex~ept as noted otherwise in Table I.
2000 gm Polyol A
30.6 gm maleic anhydride (0.8 equivalents per mole of Polyol A) gm catalyst B 200 ppm calcium 96 gm ethylene oxide (0~01 percent maximum water ) * Trademark -27-~;$
~z~s A 3-liter round-bot~om flask with a stirrer, thermometer and gas inlet was charged with polyol A, maleic anhydride and calcium naphthenata. The contents were heated to 125C and allowed to react for 1 hour. This intermediate was transferred to a l-ga~llon steam heated stainless steel autoclave. After heating to 125C and pressurizing the reactor to 34 psig with nitrogen, ethylene oxide was added during 1 hour and the mixture was reacted for 8 hours. The product was isolated after discharging by stripping the 10volatiles at 105C for 1 hour at <10 mm ~g. This product is designated as polyol D.
Procedure B
Charges: To reactor: 50 g polyol D
925 g polyol B
2.0 g initiator A
Stream #1: 260 g acrylonitrile 790 g styrene 13.5 g l-dodecanethiol Stream #2: 975 g polyol B
20 10.5 g initator A
Reaction Conditions: reaction temperature, 90C; monomer addition time, 210 minutes; polyol initiator addition time, 220 minutes; reaction time, 30 minutes; 300 rpm stirring.
The reactor charges were added to a 5-liter 4-neck flask fitted with a stirrer, nitrogen inlet, addition tube, water condenser and thermowell. After heating the polyol reaction mixture to 90C and holding for 30 minutes under nitrogen, the streams #l and $2 were added through a Kenics static mixer over the specified time period. Upon comple-tion of stream #l addition, the reaction mixture was heated to 110C and reacted for the specified time. After the reaction period was completed, the reaction mixture was vacuum stripped for 30 minutes at 115C and 1 mm Hg. The polyol from this procedure is designated as polyol J.
Procedure C
Charges: 400 lbs. polyol A
7.72 lbs. maleic anhydride 17.24 lbs. ethylene oxide The indicated amount of polyol A was charged to a clean, dry, nitrogen purged 90-gallon reactor, sealed and heated to 110C. The polyol was then flash stripped at less than 10 mm Hg into a cleanr dry 60-gallon reactor. Strip-ping was continued until the residual water level had beenreduced to 0.01 weight percent. After stripping was completed, maleic anhydride was added to the polyol, the reaction mixture was padded with 34 psi nitrogen and then :~fZZ~S
heated to 150C. AEter reacting for 4 hours, excess ethylene oxide was added over 5 hours at 150C. This reaction mixture was allowed to react 8 to 12 hours or until the acid number had dropped below 0.2 mg KOH/g. The mixture was then stripped to remove excess ethylene oxide. This product was designated as polyol E.
Procedure D
Charges: To reac~or: 10.67 lbs~ polyol E
93.33 lbs. polyol B
0.053 lb. morpholine 0.21 lb. initiator A
Stream #1: 28.0 lbs. acrylonitrile 84.0 lbs. styrene 1.12 lbs~ l-dodecanethiol Stream #2: 104.0 lbs. polyol B
1,12 lbs. initiator A
Reaction Conditions: reaction temperature, 90C; monomer addition time, 210 minutes; polyol-initiator addition time, 220 minutes; reaction time, 30 minutes.
The reactor ch~rges were added under a nitrogen atomsphere to a 50-gallon reactor. After heating the polyol reaction mixture to 90C and holding for 30 minutes, streams #1 and #2 were added through a Kenics static mixer over the specified time period. Upon completion of stream #l addition, the reaction mixture was heated to 110C and 12~ S
reacted for the specified time. After the reaction period was completed, -the reaction mixture was vacuum stripped for 3 hours at 125C and 5 mm Hg. This product is designated as polyol G.
Procedure E
Charges: To reactor~ 85.3 lbs. polyol C
26.7 lbs. polyol A
0.19 lb. initiator A
Stream #1: 24 lbs. acrylonitrile 72 lbs. styrene 0.96 lb. l-dodecanethiol Stream ~2: 112.0 lbs. polyol C
0.96 lb. initator A
Reaction Conditions: reaction temperature, 90C; monomer addition time, 180 minutes; polyol-initiator addition time, 190 minutes; reaction tim~, 30 minutes.
. The same reaction procedure was used here as in procedure D.
This product is designated polyol I.
~s~
Examples 1-17 The products of these exam~les were prepared employing various catalystsl at various concentrations and at variable maleic anhydride contents using procedure A.
~2~59~5 .~U o o o o In o o u~ O c~ o o o o o o o O O ~ O CO l~ CJ~ ~ ~ ~ ~ ~ ~`
u~ ~ o~ ~ ~ ~ o ~r ~ ~ o o~ ~ ~ el~ O O
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a) g o Examples 18-41 The products listed in Table II and III were prepared by procedure B emplo~ing the indicated polyols, monomers and concentrations.
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Examples 42-93 Examples 48 and 52 were prepared by adding to a 500 ml flask fitted with a stirrer and a nitrogen inlet tube, 700 grams of polyol E and 0.7 grams of morpholine.
The reaction mixture was heated to 90C for 1 hour, then vacuum stripped for 30 minutes at 1 mm Hg pressure.
Analysis by nuclear magnetic resonance showed 0.85 moles of fumarate unsaturation. This product was used in preparing the products of Examples 48 and 52. The remainder of the examples were prepared employing procedure D.
S4~S
m ~ ~ ~ 2 " ~ o 8 ~ ~ 1~ ~ o~ ~ o ~ ~ ~ ~`
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~ r ~ ~
~ CO L') 00 OQ 0 _I r-l r~l aJ ~ ~ o -l ~ o o o o o o o o o ~ o o o o o ~n ~o ~5~
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~ U
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:~ ~ $
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~ $ ~ a~
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~5~
Examples_94-110 The products of Table V were prepared employing procedure E except products of Examples 111 and 112 where polyol E was replaced by polyol A.
-~2-~t.
o ~ o o o o o o C~ o ~ o o o o o o o ~ ~Oæ ~
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~.22~ 5 Examples 111-127 The polyurethane foams of Tables VI, VII and VIII
were prepared by charging a cne 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.
Tables VI, VII and VIII set 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 California No. 117 open flame test, indicate that flame retardancy may be obtained with reasonably low levels of flame retardant compounds employin~ the polymer dispersions of the instant invention.
12'254BS
TABIE VI
EKample 111 112 113 114 115 116 Polyol G G G F F F
E~rnulation, p~w Polyol 100.0 q~lE~LIN~01 3, 0 6.0 12.0 3.0 6.0 12.0 RE~r ~lue X-44 0~25 GoS 1~0 0~25 0~5 1~0 ~ater 2. 8 -- --1 0 ~*TL O . 11 T-10 û. 4~
D~P 0.~ ____ TDI 37.1~------Foam Pro~erties Den~ity, pcf ~.18 2.25 2.24 2.17 2.19 2.33 Tensile strength, psi 23.3 25.8 25.6 28.1 2~.4 27.8 Elon~ation, % 77 87 110 73 90 93 Tear, pi 20~ 2.3 3.1 2.0 201 2.5 2 0 P~silienoe, % 30 26 28 32 24 26 ILD, lb/~0 sq.in. (4 inch) 2s% 118.0112.0 10~.0 124.0 116.4 110.0 65% 247.2231.6 211.6 264.0 242.0 232.4 25~6 retllrn 69.2 67.2 57.2 68.8 64.4 62.8 Sag factor 2.09 2.07 2.07 2.13 2.08 2.11 Guide factor 54.1 49.8 45.5 57.1 53.2 47.2 ~very, % 5~.0 60.0 ~6.0 55.0 55.0 57.~
50~ 57.1 71.3 89.7 14.5 58~2 72.0 9096 81.1 95.7 9~1.0 83.4 95.8 96.8 30 ~nid aged 5 hrs. at ~50F
CLD, % of ori~3inal 5096 61.1 71.0 7~.0 80.0 84.0 79.0 ~npression sets, %
50P6 57.4 66.9 87.0 25.4 57.7 66.1 90~ 76.3 92.9 97.6 26.2 83.8 ~0.2 Heat aged 22 hrs.
at 284~F tensile strength ,psi 29. 631. 8 31. 6 31. 5 33. 034 . 9 Air flowi c~n 3.80 0086 0.~5 1.92 1.10 1.10 Foam ~olor white tan *Trade mark ~`. ' '~
.:J
~Z'~5 ~r~sLE VI - continued Exa~le 117118 119 120 121 122 Polyol G G G F F F
Water 2. 8~
DE-71 6~0------------- ~~~ - ~ ~~~~~~ -~ERMOLIN 101 3.0 600 12.0 3.0 600 12.0 CALIFOKNIA NO. 117 SECTION A PART I -- OPEN FI~ME TEST
.
Spec.
Original Max.
Afterflame, sec.
10average 5.0 18~6 2.6 2.630.034.037nO
maximum 10.0 22~0 4~0 3~032~035~038.0 Char length, in.
average 6.0 5~4 2~6 2~612.012.012.0 maxim~n 8.0 6.0 3~3 20912.0120012.0 Heat aged 24 hrs./220F
Afterflame, sec.
average 5.0 16.8 3.4 3.232.035~038~0 maximum 10.0 20~0 4~0 4~032~035~03~0 Char length, in.
20average 600 5~3 2~7 2~612~012~012~0 maximum 8.0 5.9 3.0 3.012~012~012~0 CALIFORNIA NO~ 117 SECTION D PART~ II -- S~LDERING SCREENING TEST
.
Spec.
Min.
Non smoldered residue, % 80.0 93.8 97.3 97.7 bumed co~pletely BurL~ CHI~EY
~eight retention,96 69.1 92.7 95~5 0 63~0 941~5 Flame height,cm 25+ 22 19 25+ 25+ 20+
DOC FF-1--70MENqHE~sMINE PILL ~ME TEST
Spec.
3 o Min.
Inches bun.ed fromouter ring >1 2.93~4 3~3 2.9 3.2 3.1 OXYGEN INDEX
% 2 19.721.3 24.3 1~.7 20.9 21~5 --46~
TABLE VII
BLENDS OF POLYOL I/ POLYOL H
Example 123 124 Formulation .
Eblyol I 30 30 Pblyol H 70 70 Water 2.0 2.0 DEOA 0.8 0.8 L 5043 0.8 0.8 TffERMOLIN 101 3.0 3.0 T-12 0.06 0.06 ~BCO 33L~l 0.18 0.18 NIAX A-l 0.06 0.06 TDI index 108 108 California No. 117 Section A Part I - Open Flame Tbst Sp~c.
Max.
Afterflame, sec.
average 0.7 0.7 5.0 maximum 0.8 0.8 10.0 Char length, in.
average 2.1 2.3 6.0 maximum 2.2 2.5 8.0 California No. 117 Section D Part II - Smoldering & reening Test Spec.
Min.
Non-smoldered residue, % 86.4 89.0 80 ~,2259L~5;
TABI~ VIII
Ex~mple 125 126 127 Formulation Polyol J 100.0~
'lff~RMOLIN 101 3.0 12.0 --DE~71 -- -- 12.0 ANTIBL~ZE 19 ~ -- 5.0 Silicone Lr5720 1.0--- ~---~---- ----------Water 2.4-- -- -- -~ - ~-~ --DABCO TL 0.1-- - ---- - - -------~
T'10 0.4 0.4 3 DOP 0.8 0.8 Q.6 TDI (115 index) 32.5--- -Foam Properties Density, pcf 2.19 2,32 2.27 Tensile strength, psi 24.6 26.2 25.3 Elongation, % 70 127 100 Tear, pi 2.5 2.9 2.5 Resilience, % 26 30 32 ILD, lb/50 sq.in. (4 inch) 25% 119.2 119.6 97.0 266.4 244.4 23~.1 25% retNrn 71.2 72.0 49.2 Sag factor 2.23 2.04 2.45 Guide factor 54.4 51.6 42.7 ~eoovery, % 60.0 60.0 51.0 Compression sets, %
50% 25.4 82.4 73.9 9o% 53.4 96.1 96.2 Humid aged 5 hrs. at 250F
CLD, % of ori~inal 50% 80.0 67.0 82.0 Compression sets, ~
50~ 23.9 65.4 59.5 90~ 27.7 95.6 9205 Heat aged 22 hrs. at 284F
tensile strength, psi 33.5 30.6 30.1 Air flow, cfm 0.53 0.50 0.50 Color white ~,,2S~8S
TABLE VIII - c~on~inued EXample 125 126 127 CALIFORNIA NO. 117 SECTION A PART I - OPEN FLAME TEST
Spec.
Original Max.
AEterflame, sec.
average 5.0 19.4 1.6 1 6 maximum 10.0 26.0 3.0 2.0 Char length, in.
average 6.0 7.8 2.0 2.4 maximum 8.0 9.0 3.1 3.0 ~leat aged 24 hrs./220F
Afterflame, sec.
average 5.0 15.2 1.4 1.2 maximum 10.0 21.0 3.0 2.0 Char length, in.
average 6.0 6.5 2.3 2.8 maximum 8.0 8.7 3.1 3.1 CA~IFORNIA NO. 117 SECTION D PART II - SMDLDERING SCREENING TEST
.
Spec.
Max.
Non-sm~ldered residue, % 80.0 96.6 99.2 99.9 BUTLER CHIMNEY
Weight retention, % 34.6 94.3 92.9 Flame height, cm 25+ 17 14 Spec.
Min.
Inches burned from outer ring >1 3.5 3.3 3.1
Claims (9)
1. In a process for the preparation of a white stable, graft polymer dispersion which comprises the poly-merization in a conventional polyol of an organic compound having both ethylenic unsaturation and a hydroxyl, carbonyl, anhydride, isocyanate or epoxy group, the improvement which comprises conducting the polymerization in a polyol mixture containing from 0.001 to 0.09 mole of induced unsaturation per mole of said conventional polyol.
2. A white stable graft polymer dispersion com-prising a polymerized ethylenically unsaturated monomer or mixture of monomers in a macromer, said macromer being pre-pared by the reaction of a conventional polyol with an organic compound having both ethylenic unsaturation and a hydroxyl, carboxyl, anhydride, isocyanate or epoxy group, said macromer containing from 0.001 to 0.09 mole of induced unsaturation per mole of said macromer.
3. In a process for the preparation of a flame retardant polyurethane foam prepared by the reaction of an organic polyisocyanate, a polyol, a blowing agent, and flame retardants the improvement which comprises emplying the graft polymer dispersion of claim 2.
4. In a process for the preparation of a white stable, low viscosity graft polymer dispersion which comprises the polymerization in a polyol mixture of from 25 to 60 weight percent based on the total weight of the polymer dispersion of an ethylenically unsaturated monomer, or mixture of said monomers, the improvement which comprises conducting the polymerization in a polyol mixture containing from 0.001 to 0.09 mole of induced unsaturation per mole of said polyol mixture.
5. A white stable, graft polymer dispersion com-prising from about 25 to 60 weight percent based on the total weight of the polymer dispersion of a polymerized ethylenically unsaturated monomer or mixture of monomers in a polyol mixture containing from 0.001 to 0.09 mole of induced unsaturation per mole of said mixture.
6. In a process for the preparation of a flame retardant polyurethane foam prepared by the reaction of an organic polyisocyanate, a polyol, a blowing agent and a flame retardant the improvement which comprises employing the graft polymer dispersion of claim 5.
7. In a process for the preparation of a white stable, graft polymer dispersion which comprises the poly-merization in a conventional polyol of from 25 to 60 weight percent based on the total weight of the polymer dispersion of an organic compound having both ethylenic unsaturation and a carbonyl or anhydride group, the improvement which comprises conducting the polymerization in a polyol mixture containing from 0.001 to 0.09 mole of induced unsaturation per mole of said polyol mixture.
8. A white stable, graft polymer dispersion com-prising from 25 to 60 weight percent based on the total weight of the polymer dispersion of a polymerized ethylenically un-saturated monomer or mixture of monomers in a macromer said macromer prepared by the reaction of a conventional polyol with an organic compound having both ethylenic unsaturation and a carboxyl or anhydride group, said macromer containing from 0.001 to 0.09 mole of induced unsaturation per mole of said macromer.
9. In a process for the preparation of a flame retardant polyurethane foam prepared by the reaction of an organic polyisocyanate, a polyol, a blowing agent, and a flame retardant the improvement which comprises employing the graft polymer dispersion of claim 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000448076A CA1225485A (en) | 1984-02-22 | 1984-02-22 | Process for the preparation of white graft polymer dispersions and flame-retardant polyurethane foams |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000448076A CA1225485A (en) | 1984-02-22 | 1984-02-22 | Process for the preparation of white graft polymer dispersions and flame-retardant polyurethane foams |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1225485A true CA1225485A (en) | 1987-08-11 |
Family
ID=4127259
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000448076A Expired CA1225485A (en) | 1984-02-22 | 1984-02-22 | Process for the preparation of white graft polymer dispersions and flame-retardant polyurethane foams |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1225485A (en) |
-
1984
- 1984-02-22 CA CA000448076A patent/CA1225485A/en not_active Expired
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