Patent GB-954792-A (GB)
Title: Improvements in and relating to urethane polymers
IPC: C08G18/50
Filed: 1960-04-14
Abstract: In Example 9 a propoxylated dibutyl pyrophosphoric acid of OH number about 210 is prepared by reacting P2O5 with butyl alcohol and treating the product with propylene oxide.ALSO:A process for the production of a polyurethane having fire-retardant properties comprises reacting a polyisocyanate with a mixture of a polyether or polyester with a phosphorus compound having at least two active hydrogen atoms per molecule and being the reaction product of an acid of phosphorus as defined and an alkylene oxide, unless that acid is already the product of a reaction of an alkylene oxide in which case the acid itself is used, the phosphorus compound being present in an amount of at least 5% by weight of the polyester or polyether, and curing the reaction product which is formed. The reaction product may be foamed before curing, to form a cellular polyurethane. The term "acid of phosphorus" is used to mean both organic and inorganic acids and esters of phosphorus containing at least two active hydrogen atoms per molecule.  Compounds containing phosphorus which are specified, either for reaction directly or with previous reaction with an alkylene oxide, as appropriate, are, in the case of those containing two active hydrogen atoms per molecule: phosphorous acid, mono-esters of phosphoric acid, phosphonic acids, diesters of pyrophosphoric acid, diphosphinic acids, diesters of diphosphoric acids, diesters of diphosphonic acids, and addition products of these compounds with an alkylene oxide <FORM:0954792/C3/1> where R11 represents H, CH3, C2H5 or CH2Cl The esterifying groups in such esters can be substituted or unsubstituted alkyl or aryl groups, and in the case of those containing more than two active hydrogens, phosphoric acid, pyrophosphoric acid, polyphosphoric acids, monoesters of pyrophosphoric acid, diphosphonic acids and their monoesters, diphosphoric acids and their monoesters, reaction products of P2O5 with a glycol, polyglycol (with or without an alcohol), polyhydroxy compound, and reaction products of these with: <FORM:0954792/C3/2> Groups joining the phosphorus atoms in the diphosphinic, diphosphonic and diphosphoric acids include alkylene or arylene radicals or a series of such radicals separated by heteroatoms. The alkylene oxide adducts of either type can be reacted with P2O5 and the resulting products then be reacted with additional alkylene oxide. The phosphorus compounds may also contain the groups -R-OH, -RSH, -RNHR1, -RNH2, -RCOOH, -RCO.N, -RCO.NHR1 or -RCO.NH.CO.NH2 where R represents an alkylene or arylene radical or series of these separated by heteroatoms and R1 represents H, alkyl or aryl. In typical examples (i) a prepolymer prepared in a nitrogen atmosphere from propoxylated phosphoric acid and excess tolylene diisocyanate is mixed with additional propoxylated phosphoric acid, a polyether triol, CCl3F, dibutyl tin laurate and an organosilicon block copolymer surfactant.  Additional CCl3F and dibutyl tin dilaurate is mixed in and reaction to give a foam occurs; (5) the prepolymer is prepared from phthalic-adipic polyester polyol diisocyanate and in the foaming propoxylated dibutyl pyrophosphoric acid is present as a reactant; (6) in a process similar to that of (1) foaming is effected with water using an N-methylmorpholine catalyst; (9) the prepolymer is prepared by reacting tolylene diisocyanate with a mixture of propoxylated dibutyl phosphoric acid, polypropylene glycol and a tetrol [H(C2H4O)y (C3H6O)x]2 -N-CH2CH2-N[(C3 H6O)x (C2H4O)yH]2 where y is approximately 6 and x is approximately 12, foaming being effected with water; (11) coatings and films are prepared from a polyether triol, a triol/tolylene diisocyanate prepolymer, propoxylated dibutyl pyrophosphoric acid and dibutyl tin dilaurate; (13) a moulding is prepared by pouring a mixture of the prepolymer of Example 1, propoxylated phosphoric acid and dibutyl tin dilaurate into a mould and allowing to set. In Example (9) the propoxylated dibutyl pyrophosphoric acid is prepared by reacting P2O5 with butyl alcohol and treating the product with propylene oxide. Reference is also made to ethoxylated and propoxylated alkyl and aryl acid phosphates and dialkyl and aryl pyrophosphoric acids; reaction products of P2O5 with glycols, hydroquinone, bisphenol, polyethylene glycols, which products are subsequently reacted with alkylene oxides; reaction products of P2O5 with glycols and hydroxy compounds such as water and alcohols which can be subsequently reacted with alkylene oxides or epichlorhydrin, alkoxylated reaction products of P2O5 with hexanetriol, glycerol or pentaerythritol; and products obtained by reacting the above alkoxylated products with P2O5 and subsequent alkoxylation or reaction with epichlorhydrin. Specifications 821,342 and 954,793 are referred to.