Patent GB-788785-A (GB)
Title: Flame-proofing fibrous and filament-forming materials
Inventor: REDFARN CYRIL AUBREY
IPC: D01F11/02
Filed: 1954-05-01
Abstract: Inorganic polymeric substances suitable for flameproofing fibrous materials are prepared by subjecting a polymeric phosphohalogenonitride or a mixture of polymeric phosphohalogenonitrides to modification by hydrolysis, amination, hydrazination or any other reaction adapted to substitute a reactive group or groups for one or more of the halogen atoms, the said reactive groups being then reacted with any remaining halogen atoms of another of the polymer molecules or with the reactive groups of another of the polymer molecules.  In examples: (1) a mixture of polymeric phosphochloronitrides is heated at 150 DEG  C. in an autoclave with an excess of liquid ammonia; the excess ammonia is evaporated off when cold, leaving a pale yellow, water-soluble solid; (3) a cyclic trimeric phosphochloronitride is aminated by reaction with sodamide in suspension in liquid ammonia by heating in an autoclave at 130-175 DEG  C. for 8 hours; when cold, the excess ammonia is evaporated off, and the residue dissolved in the minimum of water necessary; (4) phosphochloronitride of mixed molecular complexity is mixed with an aqueous solution of hydrazine and the mixture is warmed until reaction commences; a white, brittle, solid polymer is formed; (5) a similar phosphochloronitride is gradually added in small portions to a well-stirred solution of hydrazine containing a minor amount of Calsolene Oil HS at 100 DEG  C. to form a precondensate syrup; (8) an oily polymer, obtained from a phosphochloronitride of mixed molecular complexity by removing crystalline cyclic bodies by extraction with petroleum ether, is dissolved in methylene chloride and added slowly with mixing to aqueous hydrazine.ALSO:Artificial filaments that are flame-proof and glow-proof are made from proteinaceous or cellulosic dopes, e.g. viscose, to which has been added an inorganic polymeric substance formed by subjecting a polymeric phosphohalogenonitride to modification by hydrolysis, amination, hydrazination, or other reaction which will substitute a reactive group for one or more of the halogen atoms of the phosphohalogenonitride, the said reactive groups being then reacted directly with the reactive groups or any remaining chlorine atoms of another of the polymer molecules or with a cross-linking agent forming a bridge between polymer chains.  In Example (4) a white brittle solid polymer obtained by reacting an aqueous solution of hydrazine with phosphochloronitride of mixed molecular complexity is ground when dry and added to viscose dope. The resulting rayon is flame-proof.  Modified polymeric phosphohalogenonitrides are made by subjecting the polymeric phosphohalogenonitride to modification by hydrolysis, amination, hydrazination or other reaction adapted to substitute a reactive group or groups for one or more of the halogen atoms of the phosphohalogenonitride, the reactive groups being then reacted directly with any remaining halogen atoms of another of the polymer molecules or with the reactive groups of another of the polymer molecules or with a cross-linking agent forming a bridge between polymer chains.  The polymeric phosphohalogenonitrides may be reacted with ethylene oxide to introduce b -hydroxyethyl groups.  The cross-linking agent may be a di-isocyanate, ethylene oxide, glycerol, a glycol, di- or polyhydroxy aromatic compounds, formaldehyde, glyoxal, tetrakis-hydroxy methyl phosphonium chloride, or a methylol melamine.  In examples: (2), a mixture of polymeric phosphochloronitrides is heated at 150 DEG  C. in an autoclave with excess of liquid ammonia; the excess ammonia is evaporated off when cold, leaving a pale yellow solid which is dissolved in water and the solution neutralized with acetic acid; an aqueous solution of tetrakis-hydroxymethyl phosphonium chloride neutralized with triethanolamine is added and the resulting mixture gels on standing; (11) an oily polymer, obtained from a phosphochloronitride of mixed molecular complexity by removing crystalline cyclic bodies by extraction with petroleum ether, is dissolved in methylene chloride and reacted on cloth with glycerol in ammoniacal solution, or with resorcinol or hydroquinone; (12) a phosphochloronitride of mixed molecular complexity is gradually added in small portions to a well-stirred solution of hydrazine containing a minor amount of Calsolene Oil HS at 100 DEG  C. to form a precondensate syrup which is mixed with a partly methylated methylol melamine, the mixture being applied to cloth and baked thereon; (13) phosphochloronitride of mixed molecular complexity is mixed with pyridine and dissolved with evolution of heat; a mixture of ethylene diamine hydrate and pyridine is added slowly with stirring; after a vigorous reaction, an infusible, insoluble, non-inflammable brown polymer separates out; (14) phosphochloronitride of mixed molecular complexity is suspended in water and warmed with ethylene diamine hydrate to yield, after a vigorous reaction, a white, insoluble polymer; (15) the phosphochloronitride-ammonia reaction product of Example (2) is refluxed with diethylamine and chloroform to remove ammonium chloride and, after drying, heated with toluylene di-isocyanate; a brittle, greyish-yellow solid wax is formed.