Patent GB-919067-A (GB)
Title: Phosphorus containing polyurethane foams
Inventor: HINDERSINN RAYMOND RICHARD
IPC: C08G18/38
Filed: 1961-07-10
Abstract: A process for the production of a fire resistant cellular reaction product comprises reacting (1) a hydroxyl-containing polymer having a hydroxyl number of between about 25 and 900, (2) an organic polyisocyanate, and (3) from 5 to 30% by weight, based on the weight of the hydroxyl-containing polymer of a phosphorus acid or a partially esterified phosphorus acid or mixtures thereof.  The hydroxyl-containing polymer may be a polyester, polyether or mixtures thereof.  As a modification an organic diisocyanate is first reacted with a polyester to form a prepolymer and this prepolymer is then reacted with a polyether and/or further polyester and with the phosphorus acid or partially esterified phosphorus acid.  The polyesters may be prepared from malaeic, fumaric, phthalic, tetrachlorophthalic, oxalic, malonic, succinic, glutaric or adipic acids, or Diels-Alder adducts of hexahalocyclopentadiene and a polycarboxylic compound.  As hydroxy compounds there may be used glycols, triols, pentaerythritol or a Diels-Alder adduct of a hexahalocyclopentadiene and a polyhydric alcohol.  The polyethers are reaction products of a polyhydric alcohol or polycarboxylic acid with an epoxide such as ethylene, propylene, butylene or isobutylene oxides, 2,3-epoxyhexane, 3-ethyl-2,3-epoxyoctane, epichlorhydrin, epibromohydrin, styrene oxide, glycidyl ether, methyl glycidyl ether, phenyl glycidyl ether, butyl glycidyl sulphide, glycidylmethyl sulphone, glycidyl methacrylate or acrylate, benzoate, acetate, octanoate, or sorbate, glycidyl allyl phthalate, phenyl-(p-octadecyloxybenzoyl) ethylene oxide and compounds of the formulae <FORM:0919067/IV(a)/1> Gas is formed by reaction of the polyisocyanate with the phosphorus compound, but as an additional foaming agent there can be used fluorochlorohydrocarbons; tertiary alcohols in the presence of strong acids; secondary alcohols alone or with acids; polycarboxylic acids, or anhydrides, dimethylol ureas, polymethylol phenols, formic acid or tetrahydroxymethylphosphonium chloride.  As phosphorus acids there are listed, phosphoric, phosphorous, and hypophosphorous acids and a number of phosphonic, phosphinic, and phosphonous acids, primary and secondary phosphates and phosphites, and primary phosphonates and phosphonites.  Specified fillers and additives are clay, calcium sulphate, ammonium phosphate, dyes, fibrous glass, asbestos or synthetic fibres.  In examples foams are prepared by reacting (1) (A) a mixture of a trimethylolpropane-propylene oxide reaction product, a polyester from trimethylolpropane and 1,4,5,6,7,7-hexachlorobicyclo-(2.2.1)-5-heptene-2,3-dicarboxylic acid and mono- and di-butyl phosphates with (B) a solution of trichlorofluoromethane and a reaction product of 1,4,5,6,7,7-hexachlorobicyclo-(2.2.1)-5-heptene-2,3-dicarboxylic acid and toluene 2.4- and 2.6-diisocyanates; (2) similar reactants but with the use of phosphorous acid in place of the butyl phosphates; (3) a mixture of a glycerine/adipic acid/1,4,5,6,7,7-hexachlorobicyclo-(2.2.1)-5-heptene-2, 3-dicarboxylic acid polyester, a trimethylolpropane/adipic acid polyester mono- and dibutyl phosphates and trichlorofluoromethane with a semi-prepolymer from a portion of the chlorine containing polyester and toluene diisocyanates; (4) an adipic acid/phthalic anhydride/trimethylolpropane polyester with other reactants and procedures as specified in Example (3).  In other examples the procedure of Example (1) is followed using as the phosphorus compound (8) phosphoric acid, (9) phenylphosphonic acid, (10) dimethylphosphinic acid, (11) methylphosphonous acid, (12) phenylphosphoric acid, (13) methyl ethyl phosphoric acid, (14) butyl phosphorus acid.  Specification 873,974 is referred to.ALSO:A process for the production of a fire-resistant cellular reaction product comprises reacting (1) a hydroxylcontaining polymer having a hydroxyl number of between about 25 and 900, (2) an organic polyisocyanate, and (3) from 5 to 30% by weight, based on the weight of the hydroxyl-containing polymer of a phosphorus acid or a partially esterified phosphorous acid or mixtures thereof.  The hydroxyl-containing polymer may be a polyester, polyether or mixtures thereof.  As a modification an organic diisocyanate is first reacted with a polyester to form a prepolymer and this is then reacted with a polyether and/or further polyester and with the phosphorous acid or partially esterified phosphorous acid.  Components are listed for the preparation of the polyesters and include Diels-Alderd adducts of a bexahalocyclopentadiene with a polycarboxylic acid or with a polyhydric alcohol.  Compounds list for reaction with polyalcohols or polycarboxylic acids in the preparation of polyethers include epoxides containing halogen, ether, sulphide, sulphone, ester, amino and sulphonamide groups.  Gas is formed by the reaction of the polyisocyanate and the phosphorus compound, but as an additional foaming agent there can be used fluorochlorohydrocarbons; tertiary alcohols in the presence of p  strong acids; secondary alcohols above or with acids; polycarboxylic acids or anhydrides, dimethylol ureas, polymethylol phenols, formic acid or tetrahydroxymethyl phosphorium chloride. As phosphorous acids these are listed phosphoric, phosphorous and hypophosphorous acids and a number of phosphonic, phosphinic and phosphonous acids primary and secondary phosphates and phosphites, and primary phosphonates and phosphonites. Specified fillers and additives are clay, calcium sulphate, ammonium phosphate, dyes, fibrous glass, asbestos or synthetic fibres.  In Example (1) a foam is prepared (1) by reacting (A) a mixture of trimethylalpropane-propylene oxide reaction product, a polyester from trimethylolpropane and 1, 4, 5, 6, 7, 7-hexachlorobicyilo -(2, 2,1)-5-heptene -2, 3-decarboxylic acid and mono-and dibutyl phosphates with (B) a solution of trichlorofluoromethane and a reaction product of 1, 4, 5, 6, 7, 7- hexachlorobicyclo- (2.2.1)-5- heptene -2, 3- dicarboxylic acid and toluene -2, 4-and 2, 6- diisocyanates.  In other examples the procedure of (1) is followed using as the phosphorus compound (8) phosphoric acid, (9) phenylphosphoric acid, (10) dimethylphosphinic acid, (11) methylphosphorous acid, (12) phenyl phosphoric acid, (13) methyl ethyl phosphoric acid, (14) butyl phosphorous acid.  Specification 873,974 is referred to.