Patent GB-767979-A (GB)
Title: Poly n-chlorophosphonitrilates
IPC: C11D3/395
Filed: 1954-06-09
Abstract: Poly N-chlorophosphonitrilates of general formulae <FORM:0767979/III/1> where M is a metallic ion of valency 1 or 2 and v the valency thereof, n is an integer of 3 to 7 inclusive and a is an integer 1 to n, are prepared by reacting a mono or divalent metal salt of a trito septaphosphonitrilate with sufficient hypochlorous acid or a water soluble hypochlorite of the mono or divalent metal at a pH of 3 to 11 to replace at least one hydrogen of the phosphonitrilate.  Alternatively a tri to septa phosphonitrilic acid may be reacted with a water soluble hypochlorite within the same pH range.  The polyphosphonitrilic acid or polyphosphonitrilates may be obtained by hydrolysis of the corresponding phosphonitrilic chlorides.  The latter may be prepared by the reaction of ammonium chloride and phosphorus pentachloride or by the chlorination of phosphorus nitrides.  Thus trisodium triphosphonitrilate, P3N3H3Na3O6 yields trisodium tri N-chlorophosphonitrilate, P3N3Cl3Na3O6, when all the hydrogen has been replaced by chlorine.  The reaction preferably takes place in the presence of a buffer such as disodium hydrogen phosphate, tetra sodium tetra borate, sodium bicarbonate or sodium tripolyphosphate.  If the reaction is effected in the presence of potassium chloride mixed crystals of the N - chlorophosphonitrilate and potassium chloride double salt results.  According to examples (1) trisodium triphosphonitrilate and glacial acetic acid were successively added to a sodium hypochlorite solution in an ice bath which maintained the temperature between 12 and 18 DEG C.  The reaction product was precipitated by the addition of ethyl alcohol and the white precipitate of trisodium tri N - chlorophosphonitrilate dihydrate was separated, dried and recrystallized.  (2) Tetrasodium tetra N - chlorophosphonitrilate was precipitated by a reaction analogous to that of (1) above whereby the nine hydrate was obtained. Depending on the conditions of evaporation and drying the fourteen or twenty-five hydrate may be obtained.  (4) Polysodium polyphosphonitrilate was prepared by hydrolising a fraction of phospho-nitrilic chloride boiling between 200 and 270 DEG C. to produce a mixture of polymers from pentato septainclusive.  The hydrolysis was effected with caustic soda in an ethyl ether/water medium.  The polysodium polyphosphonitrilate was precipitated from the water layer by ethyl alcohol, dried and then reacted with sodium hypochlorite solution to obtain polysodium poly N - chlorophosphonitrilate. (6) An ethyl ether solution of tetraphosphonitrilic chloride was hydrolised with water to obtain tetraphosphonitrilic acids which were reacted with sodium hypochlorite to obtain tetrasodium tetra N - chlorophonphonitrilate. Tetra potassium tetra N - chlorophosphonitrilates may be similarly prepared.  (8) Tripotassium triphosphonitrilate was prepared by reacting phosphonitrilic chloride trimer with potassium acetate in the presence of water and dioxane.  After hydrolysis was complete mixed crystals of tripotassium triphosphonitrilate and potassium chloride were removed by concentration and filtration and the crystals washed free of potassium chloride leaving a minor percentage of potassium chloride as a double salt with the triphosphonitrilate. The crystals so obtained were reacted with potassium hypochlorite sufficient to chlorinate two-thirds of the nitrogen whereby a double compound of the partially chlorinated trinitrilate and potassium chloride having a formulae 3P3N3Cl2H K3O6.2KCl. 10H2O, was obtained. A further example relates to the preparation of dicalcium tetra N - chlorophosphonitrilate.