Patent GB-873974-A (GB)
Title: Fire resistant foams
IPC: C08G18/68
Filed: 1957-11-22
Abstract: A foamable composition comprises (A) an alkyd resin consisting essentially of (1) an adduct of hexahalocyclopentadiene and an ethylenically unsaturated polycarboxylic compound condensed with a polyhydric alcohol or (2) an adduct of hexahalocyclopentadiene and an ethylenically unsaturated polyhydric alcohol condensed with a polycarboxylic acid and a polyhydric alcohol, at least a portion of the polyhydric alcohol used in the preparation of the alkyd resin having at least three hydroxyl groups; (B) a polyisocyanate; and (C) a foaming agent.  "Foaming agent" denotes any non-polymeric compound which will react with an isocyanate to produce a gaseous product. Examples are alcohols, polycarboxylic acids and methylol compounds (each in the presence of a strong acid catalyst), water, betahydroxy-aldehydes such as acetaldol and tetrahydroxymethylphosphonium chloride.  The acid catalyst can be inorganic, organic or a Lewis type acid.  The preferred acid adduct is 1, 4, 5, 6, 7, 7-hexachlorobicyclo-(2,2,1)-5-heptane-2, 3-di carboxylic acid or its anhydride or monomethyl ester.  Others are 1, 4, 5, 6, -tetrachloro-7, 7-difluorobicyclo-(2,2,1)- 5-heptane-2, 3-dicarboxylic acid; 1, 4, 5, 6, 7, 7-hexachlorobicyclo(2,2,1)- 5-heptene- 2-acetic- 2-carboxylic anhydride and 1, 4, 5, 6, 7, 7-hexachlorobicyclo-(2,2,1)- 5-heptene-2, 3-dicarbonyl chloride. Polyhydric alcohol adducts referred to are 2, 3-dimethylol-1, 4, 5, 6, 7, 7-hexachlorobicyclo(2,2,1)- 5-heptene; 2, 3-dimethylol-1, 4, 5, 6,-tetrachloro-7, 7-difluorobicyclo-(2,2,1)- 5-heptene; 2, 3-dimethylol-1, 4, 5, 6, 7, 7-hexabromobicyclo-(2,2,1)- 5-heptene; 3-(1, 4, 5, 6-tetra chloro-7, 7-difluorobicyclo-(2,2,1)- 5-heptene- 2-yl)-methoxy-1, 2-propane diol.  As alcohols with at least three hydroxy groups glycerol, hexanetriol, butanetriol, trimethylolpropane or -ethane and pentaerythritol can be used.  Some ethylene glycol or butane-1, 4-diol can also be present in the mixture.  A proportion of an aliphatic acid, e.g. oxalic, malonic, succinic, glutaric, pimelic, suberic, azelaic, sebacic, maleic, citraconic and itaconic acids is generally present in the alkydforming mixture. Before the foaming the alkyds are liquefied by heating, suitably with the addition of chlorinated esters of fatty acids or phosphate, phthalate and adipate esters.  In the products there may be incorporated antimony oxide, clay, calcium sulphate, ammonium phosphate, dyes, fibrous glass, asbestoc or synthetic fibres.  In Examples A(1) an alkyd is prepared by reacting glycerol, 1, 4, 5, 6, 7, 7-hexachlorobicyclo-(2,2,1)-5-heptene-2, 3-dicarboxylic acid and adipic acid.  To it are added with heating dioctyl sulphosuccinate, 2, 4- and 2, 6-tolylene diisocyanates, and then, at 70 DEG C. aqueous polyoxyethylene sorbitan monolaurate solution, the mixture reacting to give a cellular product.  In Example (2) there are added to the alkyd a mixture of methyl pentachlorostearate and epoxidized soy bean oil and a foaming agent comprising t-amyl alcohol and concentrated sulphuric acid. Other foaming agents illustrated include 2-methyl-, 4-pentanediol, 2-butanol, 1, 1-dimethyl- 2-phenethyl alcohol, 1, 4-butanediol, 1, 4-butenediol, 1-phenyl-1, 2-ethanediol, acetaldol and chloral hydrate, each containing conc. sulphuric acid.  Also described are mixtures of t-amyl alcohol with additions, respectively, of phosphoric, p-toluene sulphonic, picric, hydrochloric and nitric acids, and aluminium trichloride.  In further examples portions of a mixture of the alkyd of 1A and a prepolymer obtained by reacting some of the alkyd with tolylene diisocyanates are foamed by heating with further diisocyanate and, respectively, phthalic or maleic anhydride, isosebacic acid and adipic acid. Other foaming agents specified are dimethylol urea, 3, 5-diisopropyl-2, 6-dimethylol phenol, 4-t-octyl-2, 6-dimethylol phenol, bis-(3, 5-diisopropyl-1-hydroxy- 6-methylol phenol).  In Example (40) the alkyd employed is one obtained by reacting 2, 3-dimethylol-1, 4, 5, 6, 7, 7-hexachlorobicyclo-(2,2,1)- 5-heptene, glycerol and phthalic anhydride.  Specifications 746,063 and 873,975 are referred to.ALSO:Methylol phenols, for use as foaming agents (see Group V) are prepared by reacting one mole of the appropriate phenol with 10 moles of methanolic formaldehyde in the presence of KOH.  In this manner are prepared 3,5-diisopropyl-2,6-dimethylo phenol, and 4-t-butyl-and 4-t-octyl phenols.  Diels-Alder adducts for use in preparing alkyds are obtained from hexahalocyclopentadiene and unsaturated polycarboxylic acids, anhydrides or acid halides, or polyhydric alcohols containing olefinic unsaturation.  In Examples (40) 2,3-dimethylol-1,4,5,6, 7,7-hexachlorobicyclo-(2,2,1)-5-heptene is prepared by reacting hexachlorocyclo-pentadiene and cis-2-butenediol-1,4 in toluene in the presence of epichlorhydrin. Other compounds referred to are 1,4,5,6,7,7-hexachlorobicyclo(2,2,1)-5-heptene-2,3-dicarboxylic acid and its monomethyl ester; 1,4,5,6,7,7-hexachloro-2-methylbicyclo - (2,2,1) - 5 - heptene-2,3-dicarboxylic anhydride; 1,4,5,6-tetrachloro-7,7-difluorobicyclo - (2,2,1) - 5 - heptene - 2,3 - dicarboxylic acid; 1,4,5,6,7,7-hexachlorobicyclo(2,2,1)-5-heptene-2-acetic acid -2-carboxylic anhydride; 1,4,5,6,7,7 - hexachlorobicyclo - (2,2,1)-5-heptene-2,3-dicarbonyl chloride; 2,3-dimethylol - 1,4,5,6 - tetrachloro-7,7-difluoro(2,2,1)-5-heptene; 2,3 - dimethylol-1,4,5,6,7,7-hexabromobicyclo-(2,2,1)-5-heptene; 3-(1,4,5,6-tetrachloro - 7,7 - difluorobicyclo-(2,2,1)-5-heptene-2-yl)-methoxy-1,2-propane diol; and 3-(1,4,5,6,7,7 - hexachloro-(2,2,1)-4-heptene-2-yl)-methoxy - 1,2 - propane diol. Specifications 746,063 and 873,975 are referred to.ALSO:A foamable composition comprises (A) an alkyd resin consisting essentially of (1) an adduct of hexahalocyclopentadiene and an ethylenically unsaturated polycarboxylic compound condensed with a polyhydric alcohol or (2) an adduct of hexahalocyclopentadiene and an ethylenically unsaturated polyhydric alcohol, condensed with a polycarboxylic acid and a polyhydric alcohol, at least a portion of the polyhydric alcohol used in the preparation of the alkyd resin having at least three hydroxyl groups; (B) a polyisocyanate; and (C) a foaming agent.  "Foaming agent" denotes any non-polymeric compound which will react with an isocyanate to produce a gaseous product. Examples are alcohols, polycarboxylic acids and methylol compounds (each in the presence of a strong acid catalyst), water, beta-hydroxy-aldehydes such as acetaldol and tetrahydroxymethyl-phosphonium chloride.  The acid catalyst can be inorganic, organic or a Lewis type acid.  The preferred acid adduct is 1, 4, 5, 6, 7, 7-hexachlorobicyclo-(2.2.1)-5-heptane-2, 3-dicarboxylic acid or its anhydride or monomethyl ester.  Others are 1, 4, 5, 6, -tetrachloro-7, 7-difluorobicyclo-(2.2.1)-5-heptene-2, 3-dicarboxylic acid; 1, 4, 5, 6, 7, 7-hexachlorobicyclo-(2.2.1.)-5-heptene-2-acetic-2-carboxylic anhydride and 1, 4, 5, 6, 7, 7-hexachlorobicyclo-(2.2.1.)-5-heptene-2, 3-dicarbonyl chloride. Polyhydric alcohol adducts referred to are 2, 3-dimethylol-1, 4, 5, 6, 7, 7-hexachlorobycyclo-(2.2.1.)-5-hepteene; 2, 3-dimethylol-1, 4, 5, 6, -tetrachloro-7, 7-difluoro-bicyclo-(2.2.1)-5-heptene; 2, 3-dimethylol-1, 4, 5, 6, 7, 7-hexa-bromobicyclo-(2.2.1.)-5-heptene; 3-(1, 4, 5, 6-tetrachloro-7, 7-difluorobicyclo-(2.2.1) -5-heptene-2-y10-methoxy-1, 2-propane diol.  As alcohols with at least three hydroxy groups glycerol, hexanetriol, butanetriol, trimethylolpropane or-ethane and pentaerythritol can be used. Some ethylene glycol or butane-1, 4-diol can also be present in the mixture.  A proportion of an aliphatic acid e.g. oxalic, malonic, succinic, glutaric, pimelic, suberic, azelaix, sebacic, maleic, citraconic and itaconic acids is generally present in the alkyd-forming mixture.  Before the foaming the alkyds are liquefied by heating, suitably with the addition of chlorinated esters of fatty acids or phosphate, phthalate and adipate esters. In the products there may be incorporated antimony oxide, clay, calcium sulphate, ammonium phosphate, dyes, fibrous glass, asbestos or synthetic fibres.  In examples (1)A an alkyd is prepared by reacting, glycerol 1, 4, 5, 6, 7, 7-hexachlorobicyclo-(2.2.1.)-5-heptene-2, 3-dicarboxylic acid and adipic acid.  To it are added with heating dioctyl sulphosuccinate, 2, 4- and 2, 6-tolylene diisocyanates, and then, at 70 DEG C. aqueous polyoxyethylene sorbitan monolaurate solution, the mixture reacting to give a cellular product.  In example (2) there are added to the alkyd a mixture of methyl pentachlorostearate and epoxidised soy bean oil and a foaming agent comprising t-amyl alcohol and concentrated sulphuric acid. Other foaming agents illustrated include 2-methyl-, 4-pentanediol, 2-butanol, 1,1-dimethyl-2-phenethyl alcohol, 1,4-butanediol, 1,4-butendiol, 1-phenyl-1, 2-ethanediol, acetaldol and chloral hydrate, each containing cone, sulphuric acid.  Also described are mixtures of t-amyl alcohol with additions, respectively, of phosphoric, p-toluene sulphonic, picric, hydrochloric and nitric acids, and aluminium trichloride.  In further examples portions of a mixture of the alkyd of 1A and a prepolymer obtained by reacting some of the alkyd with tolylene diisocyanates are foamed by heating with further diisocyanate and, respectively, phthalic or maleic ahhydride, isosebacic acid and adipic acid.  Other foaming agents specified are dimethylol urea, 3, 5-diisopropyl-2,6-dimethylol phenol, 4-t-octyl-2,6-dimethylol phenol, bis-(3,5-diisopropyl-1-hydroxy-6-methylol phenol).  In example (40) the alkyd employed is one obtained by reacting 2, 3-dimethylol-1, 4, 5, 6, 7, 7-hexachlorobicyclo-(2.2.1.)-5-heptene, glycerol and phthalic anhydride.  Specifications 746,063 and 873,975 are referred to.