Patent GB-982931-A (GB)
Title: Organic derivatives of phosphorus isocyanates
Inventor: FIELDING HAROLD CROSBIE
IPC: C08B7/00
Filed: 1960-04-12
Abstract: The invention comprises compounds which may be polymeric of formula <FORM:0982931/C2/1> where R, R1 and R11 are residues of organic active hydrogen compounds of type HXR, HX1R1 and HX11R11 after removal of the active hydrogen containing group XH, X1H or X11H, and where R, R1 and R11 may all be the same or any two may be the same or R, R1 and R11 may together form a polymeric residue, and X, X1 and X11 are O, <FORM:0982931/C2/2> They are prepared by mixing phosphorus triisocyanate or phosphoryl triisocyanate with active hydrogen compounds, generally in the absence of moisture, and heating if necessary. Suitable active hydrogen compounds include saturated and unsaturated alcohols and amines, phenols, polyols, polyamines, polyethers, polyesters, hydrazines, ureas, oximes, amides and carboxylic acids.  Catalysts such as triethylamine or dibutyl tin acetate may be used.  The isocyanate groups may be reacted stepwise. The isocyanates may be used in the form of their phenol adducts P(NHCO.OC6H5)3 and OP(NHCO.OC6H5)3 which liberate the isocyanate on heating.  Phosphorus triisocyanate may be used in the form of its solid thermolabile polymer.  Examples describe the preparation of:-(1) OP(NHCOOC4H9-n)3; (2) OP(NHCONHCH2CH = CH2)3; (10) OP(NHCOOC4H9-n)-(NCO)2; and (11) OP(NHCOOC6H5)3.ALSO:Polymeric compounds have one of the following formulae or are derived from unsaturated monomers of such formulae: <FORM:0982931/C3/1> or <FORM:0982931/C3/2> where R, R1 and R11 are residues of organic active hydrogen compounds of type HXR, HX1R1 and H11R11 after removal of the active hydrogen-containing group XH, X1H or X11H, and where R, R1 and R11 may all be the same or any two may be the same or R, R1 and R11 may together form a polymeric residue, and X, X1 and X11 are O, <FORM:0982931/C3/3> or <FORM:0982931/C3/4> They are derived from the reaction of phosphorus triisocyanate or phosphoryl triisocyanate with active hydrogen compounds. Suitable active hydrogen compounds include alcohols, amines, polyols, polyamines, polyesters, polyethers, hydrazines, ureas, oximes, amides and carboxylic acids and naturally occurring substances such as starch, cellulose, wool protein, sugars and castor oil.  Cellulose may be used in the form of a partial acetylate or nitrate and may be reacted with excess isocyanate to give a product containing free isocyanate groups which may be further reacted with alcohols or amines. The reaction with isocyanates may be catalysed, e.g. by triethylamine or dibutyltin acetate.  The isocyanates may be used in the form of their phenol adducts, e.g. P(NHCOOC6H5)3 or O = P(NHCOOC6H5)3 which liberate the isocyanate on heating; the phenol liberated may be distilled off or reacted with paraformaldehyde or an epoxy resin.  Phosphorus triisocyanate may be used in the form of its solid thermolabile polymer. Reaction with polyesters and polyethers may be effected in the presence of water to give a foam.  The products may be formed into films, used in glass-reinforced plastics or used as textile additives.  In Example (2), PO(NHCONHCH2CH=CH2)3 is polymerized in dimethylformamide using t-butyl perbenzoate catalyst.  Other examples describe the preparation of polymers from: (3) PO(NCO)3 and dimethylglyoxime in acetonitrile; (4) P(NCO)3 and hexamethylene glycol in acetone; (5) PO(NCO)3 and hexamethylene diamine in acetone; (6) PO(NCO)3 and a diethylene glycol pentaerythritol adipate in benzene; (7) PO(NCO)3 and a glycerol-propylene oxide condensate in benzene; (8) PO(NCO)3 and a slightly branched polydiethylene adipate containing water to give a foam; (9) PO(NCO)3 and castor oil; (10) PO(NHCOOC4H9)(NCO)2 and a glycerol/propylene oxide condensate in benzene; (12) PO(NHCOOC6H5)3 and diethylene glycol pentaerythritol adipate using triethylamine as catalyst, with and without paraformaldehyde; (13) PO(NHCOOC6H5)3 and paraformaldehyde; (14) P(NCO)3 polymer and a branched polyethylene adipate; (15) PO(NCO)3 and partially hydrolysed cellulose triacetate in acetone; (16) PO(NCO)3 and partially nitrated cellulose in acetone.