Patent GB-1108006-A (GB)
Title: Process for the manufacture of neutral polyphosphoric acid ester derivatives
IPC: C07F9/09
Filed: 1965-10-28
Abstract: Mixed neutral polyphosphoric acid ester anhydrides are obtained by reacting an ester of an oxyacid of boron, carbon, silicon or sulphur or a mixture of such esters at - 78 DEG  C. to + 140 DEG  C. with P2O5.  Specified esters of oxyacids are those of the formulae <FORM:1108006/C3/1> <FORM:1108006/C3/2> <FORM:1108006/C3/3> <FORM:1108006/C3/4> wherein R is a saturated or unsaturated, oxyalkylated or halogenated aliphatic radical or an aromatic radical, R1 and R11 each represent a saturated or unsaturated, oxyalkylated or halogenated aliphatic or cycloaliphatic radical or an aromatic radical, while in Formula II R1 may also be hydrogen and R, R1 and R11 may be identical or different and may each contain 1 to 12 carbon atoms; j, k, l, m and n are whole numbers or zero and must be such that the equations given below the formulae are fulfilled and n must be greater than zero in Formulae I, II and IV and x is a whole or fractional number of at least one.  Suitable ester starting materials have the formulae B(OR)3, R1B(OR)2, R1R11 BOR, C(OR)4, HC(OR)3, OS(OR)2, R1SO2(OR), Si(OR)4, R1Si(OR)3, R1, R11Si(OR)2, R13SiOR, (RO)3Si-O-Si-(OR)3 and (RO)3Si-[O-Si (OR)2]x-O-Si(OR)3.  The ester of the oxyacid of the nonmetal, preferably in an amount of from 0.005 to 20 moles per mole of P2O5, is added in the pure state or in a solvent e.g. a halogenated hydrocarbon boiling between 35 DEG  C. and 120 DEG C. such as CHCl3, CH2Cl2, CCl3.CH3, CCl4, CH2Br2, CHCl2.CH2Cl, CH2Cl.CH2Cl, CHCL2.CH3, CCl2 = CCl2, CHCl = CCl2, CF3.CCl3 or CFCl2.CFCl2 or mixtures thereof, to P2O5 in a pure state or in one of the above solvents, preferably under an inert gas, e.g. N2, and with the exclusion of moisture.  Dissolved polyphosphoric acid ester derivatives in the mixture after completion of the reaction may be precipitated by adding a liquid precipitating agent e.g. low molecular weight alkanes and cycloalkanes containing 5 to 12 carbon atoms, aliphatic or cycloaliphatic mono- or di-ethers containing 3 to 10 carbon atoms or benzene or mixtures thereof. The products are stated to be mixed anhydrides of partially hydrolysed polyphosphoric acid esters with partially or completely hydrolysed non-metallic acid esters and to contain a mixture of open chain, cyclic and combined open chain/cyclic molecules with polyphosphate structures containing phosphorus-oxygen-non-metal bonds.ALSO:Mixed neutral polyphosphoric acid ester anhydrides are obtained by reacting an ester of an oxyacid of boron, carbon, silicon or sulphur or a mixture of such esters at a temperature within the range -78 DEG  to +140 DEG  C. with phosphorus pentoxide. Specified esters of oxyacids are those of the formulae <FORM:1108006/C2/1> <FORM:1108006/C2/2> <FORM:1108006/C2/3> wherein R is a saturated or unsaturated, oxyalkylated or halogenated aliphatic radical or an aromatic radical, R1 and R11 each represent a saturated or unsaturated, oxyalkylated or halogenated aliphatic or cycloaliphatic radical or an aromatic radical, while in Formula II R1 may also represent a hydrogen atom, and R, R1 and R11 may be identical or different and may each contain 1 to 12 carbon atoms, j, l, m, and n are whole numbers or zero and must be such that the equations given below the formulae are fulfilled and "n" must be greater than zero. Suitable esters of oxyacids of non-metals include those of the formulae B(OR)3, R1B(OR)2, R1R11BOR, C(OR)4, HC(OR)3, OS(OR)2 and R1SO2(OR).  The ester of the oxyacid of the non-metal, preferably in an amount of from 0.005 to 20 moles per mole of P2O5, is added in the pure state or in a solvent, e.g. a halogenated hydrocarbon boiling between 35 DEG  C. and 120 DEG  C. such as CHCl3, CH2Cl2, CCl3.CH3, CCl4, CH2Br2, CHCl2.CH2Cl, CH2Cl.CH2Cl, CHCl2.CH3, CCl2=CCl2, CHCl=CCl2, CF3.CCl3 or CFCl2.CFCl2 o mixtures thereof, to P2O5 in a pure state or in one of the above solvents, preferably under an inert gas, e.g. N2, and with the exclusion of moisture. Dissolved polyphosphoric acid ester derivatives in the mixture after completion of the reaction may be precipitated by adding a liquid precipitating agent, e.g. low molecular weight alkanes and cycloalkanes containing 5 to 12 carbon atoms, aliphatic or cycloaliphatic mono- or di-ethers containing 3 to 10 carbon atoms or benzene or mixtures thereof. The products are stated to be mixed anhydrides of partially hydrolysed polyphosphoric acid esters with partially or completely hydrolysed non-metallic acid esters and contain a mixture of open-chain, cyclic and combined open-chain/cyclic molecules with polyphosphate structures containing phosphorus - oxygen - non-metal bonds.