Patent GB-1002859-A (GB)
Title: Difficultly-flammable plastics obtained from phosphorus-containing isocyanates
IPC: C07F9/40
Filed: 1962-05-24
Abstract: Difficulty-flammable polyurethane plastics are prepared by reacting linear or branched condensation and/or polymerization products of molecular weight higher than 600 containing hydroxy and/or carboxy groups with phosphorus-containing polyisocyanates of formula <FORM:1002859/C3/1> where m and n are each 1, 2 or 3, R1 and R2 are aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic radicals which may contain substituents, e.g. halogen, alkoxy, nitro or alkylsulphonyl, R3 is a group derived by removal of a halogen atom from an organic or inorganic acid halide, and R4 is unsubstituted or substituted alkyl.  R3 is preferably <FORM:1002859/C3/2> but may also be derived from phosgene, carbonic acid dibromide, thiophosgene, cyanogen chloride, methyl chloroformate, acetyl chloride or other carboxylic acid chlorides, PCl3, PBr3, sulphuryl chloride or nitrosyl chloride.  Suitable hydroxy and/or carboxy containing polymers include polyethers, polythioethers, polyesters, polyester amides, polyoxyalkylated amines polyoxyalkylated amines and polyacetals.  The isocyanates may be used in the form of compounds that only liberate them when heated and polyisocyanates not containing phosphorus may also be present.  The isocyanates and the compounds containing hydroxy and/or carboxy groups may be reacted to form a prepolymer still containing free isocanate and this further reacted with compounds of molecular weight lower than 500 containing at least two active hydrogens, e.g. glycols, diamines or water. Storable products may be obtained by using excess hydroxy and/or carboxy containing compound over the isocyanate, and these later cross-linked either with phosphorus-containing polyisocyanate or with peroxides, sulphur or formaldehyde.  Foams may be obtained when excess isocyanate groups are present and a blowing agent such as water is also present, or blowing may be effected with azo compounds or haloalkanes.  Catalysts may be present, e.g. triethylenediamine, dimethylbenzylamine, Nmethyl - N1,N1 - dimethylaminoethylpiperazine, molybdenum glycolate, stannous octoate or dialkyltin compounds.  Silicone and other surfactants may be present.  Fillers may be added. Lacquers and coating materials may be prepared. Typical phosphorus-containing polyisocyanates are <FORM:1002859/C3/3> and <FORM:1002859/C3/4> Crude reaction mixtures may also be used obtained by reacting tertiary phosphite esters with crude N,N,N1-trisubstituted haloformamidines prepared by reacting an isocyanate with a carbodiimide and treating the product with an acid halide.  In Examples: (1) and (2) foams are prepared from an adipic acid/phthalic acid/oleic acid/trimethylol propane polyester; (3) a joint sealing compound is prepared from an adipic acid/diethylene glycol/trimethylol propane polyester; (4) a lacquer is prepared in ethyl acetate/butyl acetate/ethylene glycol monoethyl ether acetate/toluene solution from an adipic acid/ethylene glycol polyester; (5) a solvent free lacquer is prepared from castor oil, blown castor oil, ferric oxide, barium sulphate, sodium aluminosilicate and talcum; (6) a composition for flame-proofing fabrics is made in ethyl acetate solution from a tolylene diisocyanate modified adipic acid/ethylene glycol polyester and a diurethane catalyst prepared from N - methyldiethanolamine and phenyl isocyanate; (7) a composition for flame-proofing fabrics is made from the same polyester and disurethane as in Example (6) and a phosphorilated hydroxyl compound prepared from formaldehyde, diethanolamine and dichlorethyl phosphite, a crude phosphorus-containing isocyanate of the above described type being added in each example.  Specification 963,404 is referred to.ALSO:In example 6 a cotton fabric is coated wth several layers, drying between layers, of an ethyl acetate solution of a polyurethane resin forming composition comprising a tolylene diisocyanate modified adipic acid/ethylene glycol polyester, a diurethane catalyst prepared from N-methylol diethanolamine and phenyl isocyanate and a phosphorus-containing polyisocyanate composition obtained by treating with trichloroethyl phosphite, the mixture obtained by reacting phosgene with the reaction product of hexamethylenediisocyanate and dicyclohexyl carbodiimide.  In Example 7, a similar composition is used containing additionally a formaldehyde/diethanolamine/dichloroethyl phosphite reaction product. The phosphorus-containing polyisocyanate presumably contains, inter alia, the compound <FORM:1002859/B1-B2/1>