Patent GB-1064610-A (GB)
Title: Process for the manufacture of neutral polyphosphoric ester anhydrides
IPC: C07F9/46
Filed: 1965-10-28
Abstract: Neutral polyphosphoric ester anhydrides are obtained by reacting a phosphorus compound, or a mixture of such compounds, having the formula (R1)mP\(OR)n where n is 1 or 3 and m is 0 or 2 and m + n = 3, R1 is a saturated, oxyalkylated or halogenated aliphatic, cycloaliphatic or aromatic radical containing 1 to 10 carbon atoms and R is a saturated aliphatic or haloaliphatic radical containing 1 to 5 carbon atoms, with P2O5, optionally in the presence of a solvent, at tem peratures within the range of from - 78 DEG  C. to + 140 DEG  C. 0.01 to 20 moles of the phosphorus compounds per mole of P2O5 is preferably used and the reaction is preferably effected under an inert atmosphere, e.g. N2, suitable solvents being halogenated hydrocarbons boiling within the range of from 30 DEG  to 120 DEG  C. such as CHCl3, CH2Cl2, CCl3.CH3, CCl4, CH2Br2, CHCl2.CH3, CH2Cl1CH2Cl, CHCl2.CH2Cl, CHCl = CHCl2, CCl2 = CCl2, CF3.CCl3m or CFCl2.CFCl2 or mixtures thereof.  After completion of the reaction the products if no solvent was used are preferably dissolved in one of the above solvents and may be precipitated by the addition of a liquid precipitating agent, e.g. low molecular weight alkanes and cycloalkanes containing 5 to 12 carbon atoms which are liquid at room tem peratures, e.g. hexane, heptane, octane and cyclohexane, aliphatic and cyclic ethers such as diethyl ether, tetrahydrofuran, glycol dimethyl ether or dioxan and benzene or mixtures thereof. The products are stated to be mixed anhydrides of partially hydrolysed polyphosphoric acid esters with partially or completely hydrolysed phosphorous compounds of the above formula and to contain a mixture of open-chain, cyclic and combined open-chain/cyclic molecules with polyphosphate units containing phosphite and/ or phosphinate groups in a partially and/or completely anhydrous form.  The products may be used as polymerization catalysts in the polyacetal field.ALSO:Condensed neutral polyphosphoric ester anhydrides are obtained by reacting a phosphorus compound or a mixture of such compounds having the formula (R1)mP(OR)n, where n is 1 or 3 and m is 0 or 2 and m+n=3, R1 is a saturated, oxyalkylated or halogenated aliphatic, cycloaliphatic or aromatic radical containing 1 to 10 carbon atoms and R is a saturated aliphatic or haloaliphatic radical containing 1 to 5 carbon atoms, with P2O5, optionally in the presence of a solvent, at temperatures within the range of from - 78 DEG  to + 140 DEG  C.  The amount of the phosphorus compound used is preferably 0.01 to 20 moles per mole of P2O5 and the reaction is preferably effected under an inert atmosphere, e.g. N2, suitable solvents being halogenated hydrocarbons boiling within the range of from 30 DEG  to 120 DEG  C. or mixtures thereof. After completion of the reaction the products, if no solvent was used, are preferably dissolved in one of the above solvents and may be precipitated by the addition of a liquid precipitating agent, e.g. low molecular weight alkanes and cycloalkanes containing 5 to 12 carbon atoms which are liquid at room temperature, e.g. hexane, heptane, octane and cyclohexane, aliphatic and cyclic ethers such as diethyl ether, tetrahydrofuran, glycol dimethyl ether or dioxan, and benzene or mixtures thereof.  The products are stated to be mixed anhydrides of partially hydrolysed polyphosphoric acid esters with partially or completely hydrolysed phosphorus compounds of the above formula and to contain a mixture of open-chain, cyclic and combined open-chain/cyclic molecules with polyphosphate units containing phosphite and/or phosphenite groups in a partially and/or completely anhydrous form.  The products may be used as polymerization catalysts in the polyacetal field.