Patent GB-960368-A (GB)
Title: Polyphosphonates containing trivalent phosphorus ester groups
IPC: C08G79/04
Filed: 1960-06-16
Abstract: The invention comprises organo-phosphorus compounds of the formula:- <FORM:0960368/C1/1> in which R is an alkyl, haloalkyl, alkoxyalkyl, aryloxyalkyl alkoxyhaloalkyl, arylhaloalkyl, aryloxyhaloalkyl, alkenyl or haloalkenyl group having 1 to 12 carbon atoms, each R1 is a group having the general formula -OR in which R is as defined above, or is a hydrocarbon or halohydrocarbon group having 1 to 12 carbon atoms, Z is a hydrogen atom or a hydrocarbon, halogenated hydrocarbon, carbalkoxyhydrocarbon, alkathiohydrocarbon, alkoxyhydrocarbon or cyanohydrocarbon group having 1 to 17 carbon atoms or a furyl or thienyl group and n is an integer which is at least 1.  Each of the groups RO and R1 may conveniently have the structure Cl.CHY.CHYO-in which one Y is a hydrogen atom and the other Y is a hydrogen atom or an alkyl, haloalkyl or alkenyl group having 1 to 6 carbon atoms, a phenyl group or an alkoxyalkyl or an aryloxyalkyl group having up to 10 carbon atoms. They may be obtained by reacting a molar amount of a trivalent phosphorus halide of the formula RO.P(R1).X in which R and R1 are as defined above and X is a halogen atom, at least a molar amount of an aldehyde Z.CHO and less than a molar amount of an ester of phosphorus having the general formula (R1)2POR in which R and R1 are as defined above. Alternatively, they may be obtained by reacting a phosphorous ester of a hydroxymethyl phosphonate having the general formula: <FORM:0960368/C1/2> in which R, R1 and Z are as defined above with a trivalent phosphorus halide ROP(R1)X as defined above and at least an equimolar amount of an aldehyde ZCHO.  The aldehyde and the trivalent phosphorus halide may differ from those used to form the phosphorous ester of the hydroxymethyl phosphate so that the units:- <FORM:0960368/C1/3> need not be identical in the ester product.  The number of repeating units in the product may be up to 100.  A mixture of trivalent organic phosphorus halogen compound and a trivalent ester of phosphorus produced by reacting two moles of phosphorus trihalide with more than four but less than 5 moles of an oxirane compound, e.g. alkylene oxide, may suitably be used in the process for reaction with the aldehyde.  The reaction to form the products may be effected at ordinary or moderately decreased or increased temperature according to the nature of the reactants and in some cases heating of the reaction mixture, e.g. up to 150 DEG C. may be necessary when all the aldehyde has been added. An inert solvent or diluent, e.g. benzene, toluene, dioxane, methylene chloride or hexane may be present. Formation of the polyphosphorus compounds is accompanied by the formation of a by-product halide (RX) which may be removed by volatilisation. Several examples are given and the products are useful as lubricant and gasoline additives (see Division C5), as functional fluids in electrical and force-transmitting applications, as foam-suppressing and foam regulating agents, as biological and agricultural toxicants, as rubber compounding chemicals, as flame proofing agents for cellulosic and carbonaceous combustible materials (see Division D1) and as adjuvants, e.g. plasticizers for synthetic resins (see Division C3).  Specification 941,706 is referred to.ALSO:The invention comprises organo-phosphorus compounds of the formula:- <FORM:0960368/C3/1> in which R is an alkyl, haloalkyl, alkoxyalkyl, aryloxyalkyl, alkoxyhaloalkyl, arylhaloalkyl, aryloxyhaloalkyl, alkeynl or haloalkenyl group having 1 to 12 carbon atoms, each R1 is a group having the general formula -OR in which R is as defined above, or is a hydrocarbon or halohydrocarbon group having 1 to 12 carbon atoms, Z is a hydrogen atom or a hydrocarbon, halogenated hydrocarbon, carbalkoxyhydrocarbon, alkathiohydrocarbon, alkoxyhydrocarbon or cyanohydrocarbon group having 1 to 17 carbon atoms or a furyl or thienyl group and n is an integer which is at least 1 and may be up to 100.  Each of the groups RO and R1 may conveniently have the structure C1.  CHY. CHYO- in which one Y is a hydrogen atom and the other Y is a hydrogen atom or an alkyl, haloalkyl or alkenyl group having 1 to 6 carbon atoms, a phenyl group or an alkoxyalkyl or an aryloxyalkyl group having up to 10 carbon atoms.  They may be obtained by reacting a molar amount of a trivalent phosphorus halide RO.P(R1)X wherein R and R1 are as defined above and X is a halogen atom, at least a molar amount of an aldehyde ZCHO and less than a molar amount of an ester of phosphorus having the formula (R1)2POR. Alternatively they may be obtained by reacting a phosphorous ester of a hydroxy-methyl phosphonate having the general formula:- <FORM:0960368/C3/2> in which R, R1 and Z are as defined above with a trivalent phosphorus halide ROP(R1)X as defined above and at least an equimolar amount of an aldehyde ZCHO.  The aldehyde and the trivalent phosphorus halide may differ from those used to form the phosphorous ester of the hydroxymethyl phosphonate so that the units:- <FORM:0960368/C3/3> need not be identical in the product.  A mixture of trivalent organic phosphorus halide and a trivalent phosphorus ester obtained by reacting two moles of a phosphorus trihalide with more than four but less than 5 moles of an oxirane compound, e.g. an alkylene oxide, an haloalkyl-, alkenyl- or other appropriately substituted oxirane compound such as epichlorhydrin or a glycide ether may suitably be used in the process for reaction with the aldehyde.  The reaction to form the products may be effected at ordinary or moderately decreased or increased temperature according to the nature of the reactants and in some cases it may be necessary to heat the reaction mixture, e.g. up to 150 DEG C., when all the aldehyde has been added.  An inert solvent or diluent, e.g. benzene, toluene, dioxane, methylene chloride or hexane may be present.  The products are useful as adjuvants for synthetic resins and plastics, e.g. as flame proofing agents and plasticizers, and may be used in the preparation of phenolic, polyester, polyamide and cellulose ester resins and in polymers such as polyvinyl chloride, polyvinyl acetals, polystyrene, polyethylene, vinyl chloride-vinyl acetate co-polymers, the olefin-maleic anhydride copolymers, polybutadiene, and copolymer elastomers such as butadiene-styrene and butadiene-acrylonitrile. They may also be used in the preparation of foamed resins, e.g. polystyrene foam and polyester foams such as polyethylene terephthalate and the polyurethanes.  They may be used with a diisocyanate and an hydroxyl group containing material in a quantity of up to 40% of the mixture. The products can also be used as rubber compounding chemicals, as lubricant and gasoline additives (see Division C5), as functional fluids in electrical and force-transmitting applications, as biological and agricultural toxicants, and as flame-proofing agents for cellulosic materials (see Division D1).  Specification 941,706 is referred to.ALSO:An hydrocarbon fuel comprises gasoline, an organo-lead antiknock compound and an organophosphorus compound of the formula <FORM:0960368/C4-C5/1> in which R is an alkyl, haloalkyl, alkoxyalkyl, aryloxalkyl, alkoxyhaloalkyl, arylhaloalkyl, aryloxyhaloalkyl, alkenyl or haloalkenyl group having 1 to 12 carbon atoms, each R1 is a group having the general formula -OR in which R is as defined above, or is a hydrocarbon or halohydrocarbon group having 1 to 12 carbon atoms, Z is a hydrogen atom or a hydrocarbon, halogenated hydrocarbon, carbalkoxyhydrocarbon, alkathiohydrocarbon, alkoxyhydrocarbon or cyanohydrocarbon group having 1 to 17 carbon atoms or a furyl or thienyl group and n is an integer which is at least 1 (see Division C2).  Each of the groups RO and R1 may conveniently have the structure Cl.CHY. CHYO- in which one Y is an hydrogen atom and the other Y is a hydrogen atom or an alkyl, haloalkyl or alkenyl group having 1 to 6 carbon atoms, a phenyl group or an alkoxyalkyl or an aryloxyalkyl group having up to 10 carbon atoms.  The gasoline composition may also contain a hydrocarbon halide, e.g. ethylene dibromide or dichloride, acetylene tetrabromide, a polyhaloalkyl benzene or a monoor poly-halo-propane, -butane, or -pentane and other conventional additives.  Specification 941,706 is referred to.ALSO:Carbonaceous combustible materials, e.g. cellulosic materials such as cotton cloth, may be flame-proofed by applying thereto an organophosphorus compound of the formula:- <FORM:0960368/D1-D2/1> in which R is an alkyl, haloalkyl, alkoxyalkyl, aryloxyalkyl, alkoxyhaloalkyl, arylhaloalkyl, aryloxyhaloalkyl, alkenyl or haloalkenyl group having 1 to 12 carbon atoms, each R1 is a group having the general formula -OR in which R is as defined above, or is a hydrocarbon or halohydrocarbon group having 1 to 12 carbon atoms, Z is a hydrogen atom or a hydrocarbon, halogenated hydrocarbon, carbalkoxyhydrocarbon, alkathiohydrocarbon, alkoxyhydrocarbon or cyanohydrocarbon group having 1 to 17 carbon atoms or a furyl or thionyl group and n is an integer which is at least 1 (see Division C2).  Each of the groups RO and R1 may conveniently have the structure C1.CHY.CHYO- in which one Y is a hydrogen atom and the other Y is a hydrogen atom or an alkyl, haloalkyl or alkenyl group having 1 to 6 carbon atoms, a phenyl group or an alkoxyalkyl or an aryloxyalkyl group having up to 10 carbon atoms.  The compound may be applied to cotton cloth by padding a solution or suspension of the compound. Specification 941,706 is referred to.