Patent GB-1042622-A (GB)
Title: Phosphate polyisocyanate compositions and fire resistant products made therefrom
IPC: C08G18/38
Filed: 1963-04-02
Abstract: An ester of orthophosphosphoric acid or polyphosphoric acid having two or more functional groups with reactive hydrogen atoms is reacted with an organic polyisocyanate. The orthophosphoric acid is defined as having a strength of up to and including 100% H3PO4 and the polyphosphoric acid as having an acid strength of more than 100% H3PO4.  The esters may be prepared by (1) reaction of one of the above acids with a monomeric cyclic compound containing a three-membered heterocyclic ring in which the hetero atom is O, N or S which may be followed by chain extension and neutralization or (2) reaction of P2O5 with a polyol, polyamine or polymercaptan which may be followed by chain extension and neutralization. Monomeric cyclic compounds may be: ethylene oxide, propylene oxide; 1,2-butylene oxide, pentylene oxide, octylene oxide, octadecylene oxide, styrene oxide, phenyl glycidyl ether, butyl glycidyl ether, allyl glycidyl ether, ethylene sulphide, propylene sulphide; 1,2-butylene sulphide; 2,3-butylene sulphide; styrene sulphide, allyl thioglycidyl ether; ethylene imine; propylene imine; epichlorhydrin, epibromohydrin, and glycidol. Polyols, polymercaptans and polyamines may be: sorbitol, trimethylolpropane, pentaerythritol, propylene glycol, polypropylene glycol, ethylene glycol, polyethylene glycol, 1,2-hydroxy butane; 2,3-hydroxybutane, polybutylene glycol; bis-b -dimercaptoethyl ether and N,N,N1,N1 - tetrakis(2 - hydroxypropyl)ethylene diamine.  In Example (1) phosphoric acid is reacted with either propylene oxide or epichlorhydrin in molar ratios of monomer: acid of 5:1 to 10:1, or with polypropylene glycol (3:3:1).  In Example (2) P2O5 is reacted with propylene oxide and chain extended in a second step with more propylene oxide.  In Example (5) propylene oxide is reacted with a pentaerythritol/H3PO4 adduct.  In Examples (6) epichlorhydrin and propylene oxide are reacted with H3PO4.  (7) Propylene oxide and trimethylol propane are reacted with H3PO4. (13) Propylene oxide is reacted with the adduct of H3PO4 and sorbitol.  (14) Propylene oxide and a polyepoxide ("EPON" 828) are reacted with H3PO4.  In Example (23) the esters prepared as described above are reacted with an excess of tolylene diisocyanate to given an adduct containing free-NCO groups.ALSO:Polymers, e.g. polyurethanes or polyureas are produced by reacting an organic polyisocyanate with an ester (see Division C2) of orthophosphoric acid or polyphosphoric acid, said ester having two or more functional groups with reactive hydrogen terminals, e.g. hydroxyl, mercapto or amino groups.  The orthophosphoric acid is defined as having a strength of up to and including 100% H3PO4 and the polyphosphoric acid as having an acid strength of more than 100% H3PO4.  The esters may be prepared by the (1) reaction of one of the above acids with a monomeric cyclic compound containing a three-membered heterocyclic ring in which the hetero atom is O, N or S which may be followed by chain extension and neutralization, or (2) by reaction of P2P5 with a polyol, polymercaptan or polyamine which may be followed by chain extension and neutralization.  Monomeric cyclic compounds may be: ethylene oxide, propylene oxide; 1,2-butylene oxide, pentylene oxide, octylene oxide, octadecylene oxide, styrene oxide, phenyl glycidyl ether, butyl glycidyl ether, allyl glycidyl ether, ethylene sulphide, propylene sulphide; 1,2-butylene sulphide; 2,3-butylene sulphide; styrene sulphide, allyl thioglycidyl ether; ethylene imine; propylene imine, epichlorhydrin, epibromohydrin and glycirol.  Polyols, polymercaptans and polyamines may be: sorbitol, trimethylolpropane, pentaerythritol, propylene glycol, polypropylene glycol, ethylene glycol, polyethylene glycol; 1,2-hydroxybutane; 2,3-hydroxybutane, polybutylene glycol; bis-b -dimercaptoethyl ether and N,N,N1,N1-tetrakis-(2-hydroxypropyl) ethylene diamine. The phosphoric acid may also be esterified with polyepoxy materials, e.g. epoxidized polybutadiene materials, bisphenol A/epichlor hydrin type, cycloaliphatic type, resorcinol diglycidyl ether type, epoxynovolate type and epoxidized fatty acids.  In Example (23) an excess of tolylene diisocyanate is reacted with various esters and orthochlorobenzoyl chloride added to the reaction mixture to obtain a prepolymer. Typical esters used are the reaction products of phosphoric acid with (1) propylene oxide, (2) epichlorhydrin, (3) polypropylene glycol, (4) pentaerythritol followed by propylene oxide, (5) propylene oxide and epichlorhydrin, (6) butylene oxide, (7) sorbitol and propylene oxide, (8) propylene oxide and a polyepoxide ("EPON" 828), (9) trimethylol propane, (10) Styrene oxide, (11) dipropylene glycol. In Example (24) self-extinguishing foams were prepared from the prepolymers obtained as described above by reaction with N,N,N1,N1 tetrakis - (2 - hydroxypropyl) ethylene diamine and a phosphate ester in the presence of diethylethanolamine, triethylene diamine water and silicone surfactant.  In Example (26) esters prepared as described above were reacted with a deficiency of diisocyanate to form hydroxy functional adducts which were converted to foams by reaction with prepolymers. In Example (30) a casting was prepared from tolylene diisocyanate and the reaction product of propylene oxide and H3PO4.  In Example (31) a prepolymer derived from tolylene diisocyanate and the adduct of epichlorhydrin and H3PO4 was reacted with more of the same adduct to prepare a laminating resin, which was used to coat pieces of cloth.