Patent GB-967719-A (GB)
Title: Phosphorus compounds and a process for the preparation of polyurethane plastics using such phosphorus compounds
IPC: C07F9/12
Filed: 1961-08-25
Abstract: Hydroxyl-containing phosphorus compounds having molecular weights of 600 to 10,000 are prepared by reacting a polyhydric alcohol with a phosphoric acid ester of the formula: <FORM:0967719/C1/1> where R is an organic radical, R1 is an aromatic radical substituted by at least one aliphatic group which may be substituted by a phosphonic ester group, there being at least one halogen atom in at least one aliphatic substituent, and n is 1 to 3. The organic radical R may be alkyl, alkenyl, alkynyl, aryl, aralkyl, alkaryl, aralkenyl, cycloalkyl, cycloalkenyl and heterocyclic; many examples are given. The preferred R1 radicals are C6H4(CH2)nX, where n is 1, 2, 4 and 8, C6H3(CH2X)2 and C6H3ClCH2X, where X is halogen. These react with the polyhydric alcohols to form groups <FORM:0967719/C1/2> where Ar is arylene and R11 is derived from the alcohol. Suitable polyhydric alcohols are the glycols, tri- and higher hydric alcohols, compounds containing additionally ester, methane and urea groups, polyalkylene ether and thioether glycols, saccharides, compounds containing tertiary nitrogen atoms and alkylene oxide condensates. An alkylene oxide may be present during the reaction.  The phosphate starting materials containing at least 2 halogen atoms may be modified by reaction with a trialkyl (or haloalkyl) phosphite. The products are used for making polyurethanes (see Division C3).  Tricresyl phosphate is chlorinated using U.V. irradiation or an iodine catalyst. The product is reacted in an Arbusow reaction with trichloroethylphosphite.  Specifications 769,682, 804,369 and 819,384 are referred to.ALSO:Hydroxyl and phosphorus-containing polymers having molecular weights of 600 to 10,000 are prepared by reacting a polyhydric alcohol with a phosphoric acid ester of the formula: <FORM:0967719/C3/1> where R is an organic radical, R1 is an aromatic radical substituted by at least one aliphatic group which may be substituted by a phosphonic ester group, there being at least one halogen atom in at least one aliphatic substituent, and n is 1 to 3. The organic radical R may be alkyl, alkenyl, alkynyl, aryl, aralkyl, alkaryl, aralkenyl, cycloalkyl, cycloalkenyl and heterocyclic; many examples are given.  The preferred radicals R1 are C6H4CH2X, C6H3(CH2X)2, C6H4(CH2)nX where n is 2, 4 and 8, and C6H3ClCH2X, where X is halogen.  These react with the polyhydric alcohols to form groups: <FORM:0967719/C3/2> where Ar is arylene and R11 is derived from the alcohol. Suitable polyhydric alcohols are the glycols, tri- and higher-hydric alcohols, compounds containing additionally ester, urethane, carbonamide, and urea groups, polyalkylene ether and thioether glycols, compounds containing tertiary nitrogen atoms, condensation products of alkylene oxides, and saccharides. An alkylene oxide may be present during the reaction.  The phosphate starting materials containing at least 2 halogen atoms may be modified by reaction with a trialkyl (or haloalkyl) phosphite. The polyhydroxy compounds prepared by the invention are useful for preparing flame-resistant polyurethanes, porous or non-porous. They may be used in conjunction with compounds containing active hydrogen, e.g. polyalkylene ether polyols, hydroxyl-containing polyesters or polyhydric polythioether. A number of compounds are listed as suitable polyisocyanate reactants.  The porous products are obtained by the use of water and/or an organic blowing agent in a single or two-stage process. The usual emulsifiers and silicone stabilizers may be used, as well as catalysts, e.g. tertiary amines, tin compounds and other organo-metallic compounds. Non-porous polyurethanes are prepared using excess polyisocyanate and a cross-linking agent, e.g. polyhydric alcohol or polyamine. Coating compositions may be prepared by reacting the hydroxyl-containing phosphorus compounds with polyisocyanates in an inert organic solvent.  Pigments such as iron oxide, carbon black, titanium dioxide, zinc oxide, chrome green and lithol red may be added. Specifications 769,682, 804,369 and 819,384 are referred to.ALSO:Wood, metal, rubber, glass, paper and foamed plastics are coated, e.g. by brushing, with the reaction product in an organic solvent of an organic polyisocyanate with a hydroxyl-containing phosphorus compound having a molecular weight of 600-10,000 prepared from a polyhydric alcohol and a haloaliphatic-aryl phosphate (see Division C3).  The compositions may contain pigments, e.g. iron oxide, carbon black, titanium dioxide, zinc oxide, chrome green and lithol red.  The coatings have sound-and thermal-insulating properties.  Specifications 769,682, 804,369 and 819,384 are referred to.