Patent GB-918636-A (GB)
IPC: C08K5/5399
Abstract: 918,636. Polyurethanes containing phosphorus. PITTSBURGH PLATE GLASS CO. April 27, 1961 [May 17, 1960], No. 15240/61. Class 2(5) [Also in Group V] A method of preparing a flame-retardant polyurethane resin comprises reacting (A) an organic polyisocyanate, (B) a non-phosphorus containing polyol, (C) an organic polyol containing phosphorus and (D) an insoluble phosphorus-containing polyamide containing at least about 10% by weight of nitrogen and at least about 10% by weight of phosphorus. Foamed products can be obtained by using a gas-producing agent in admixture with the other reactants. Reactant A can be a prepolymer polyurethane containing isocyanate. groups, prepared from polyol B or C. The phosphoruscontaining polyamides contain the group usually in the structure Such compounds can be prepared by reacting phosphoryl chloride, orthophosphoric acid, phosphorus pentoxide, or phosphorus tri- or pentachloride, for example, with such nitrogen compounds as ammonia, ammonium carbonate or carbamate, urea, urea-formaldehyde condensate, melamine, melamine-formaldehyde condensate, guanidine-carbonate-formaldehyde condensate, cyanamide, dicyanodiamide, ammeline, cyanuric acid, dimethylol urea, guanidine, biguanide, biuret, ethylene imine, uric acid, diformyl hydrazine, methylamine, dimethylamine, ethylamine, propylamine, hydrazine, methyl hydrazine or ethyl hydrazine. Examples of polyamides are those obtained by reacting (A) phosphorus oxychloride and ammonia in kerosene, or phosphorus pentoxide and urea or melamine; (B) guanidine carbonate, melamine, formaldehyde. The phosphorus-containing polyol can be prepared by reacting phosphorus oxychloride or phosphoric acid with polyols. It may contain amino groups also. Many of the polyols are of the formula R 2 P(O)Z in which R may be alkoxy, aryloxy, hydroxy alkyl, -O-A-[OA] n -OH wherein A is aliphatic hydrocarbon and n is a whole number from 0 to 50, O-B(OH) m -[O-B(OH) m ] n -OH, in which B is aliphatic, m is 1 to 6 and n is 0 to 10, or -A-N(D)-A-R 1 , R 1  being H or OH, A being alkylene, D being H or aliphatic hydrocarbon. R may also represent -CH 2 -C(R  3 ) 2 G-N(R 2 OH) 2 , G being alkyl, R 2  alkyl or hydroxyalkyl, R 3  being H, OH or alkyl. Z (above) can represent H, a radical R, or a group of the formula in which R 3  is alkylene or a plurality of alkylene groups connected by ether linkages, or hydroxyalkylene. Such latter compounds are obtained by reacting phosphoric acid with a polyol and reacting the product with an alkylene oxide. Phosphorus-containing polyols are prepared in examples by (C) reacting glycerol with phosphoric acid and phosphorus pentoxide and treating the product with propylene oxide, (D) a similar process with glycol as starting material. Other polyols can be obtained by reacting a dialkyl phosphite with an alkanolamine and an aldehyde or ketone giving a compound of the formula in which M is alkylene or hydroxy alkylene R, R 1  and R 2  are alkyl, and R 1  and R 2  may also be H. The polyols not containing phosphorus may be castor oil, alone or mixed with polyethylene glycol, polyesters, polyether polyols obtained by reacting an alkylene oxide with sucrose or sorbitol. In preparing foams there may also be present in the reaction mixture foaming agents such as CCl 3 F; catalysts such as tetramethyl guanidine, triethylene diamine, DMEA, stannous octoate or oleate or dibutyltin dilaurate; surfactants of the formulae or or monoesters of higher fatty acids and silicones. In examples there are prepared two types of "packages". "Package A" comprises phosphoryl polyol, trimethylol-ethane or sucrosepolyether polyol and toluene diisocyanate (or a corresponding prepolymer) and CCl 3 F. "Package B" is made of sucrose polyol, phosphoryl polyol, phosphoryl polyamide, surfactant and catalyst. The two types are mixed together, a foamed material being obtained. Control processes in which only one of the phosphoruscontaining polyol and the phosphorus-containing polyamide is present are described.