Patent GB-951445-A (GB)
Title: Process for the manufacture of surface-active agents on the basis of derivatives of polyalkylene glycols
IPC: C09K23/00
Filed: 1960-02-24
Abstract: Tertiary phosphoric acid esters of polyalkylene glycols are prepared by reacting a compound of the formula: Z(C2H4O)x.C2H4OH in which Z is an organic radical bound to the C2H4O chain through a "functional" group and x is 1 to 10,000, with from 1/3 to 1 equivalent of phosphorus pentoxide, phosphorus oxychloride, orthophosphoric acid or a polyphosphoric acid formed by dehydrating ortho-phosphoric acid, at least the final part of the reaction being effected at a temperature above 190 DEG C. while continuously removing volatile by-products, until the reaction product becomes highly viscous and has an acid number between 0 and 4.2. The functional group joining Z to the C2H4O chain is defined as one of the following:  an oxygen or sulphur atom, a -COO-, <FORM:0951445/C2/1> , also- <FORM:0951445/C2/2> , -SO- or -SO2- radical, in which R1 is a hydrogen atom, low alkyl radical or -(CnH2n-O)m(C2H4O) xC2H 4OH, where m is 0 to 200, x is 1 to 200, m+x not exceeding 200, and n is 3 or 4.  The radical Z may be aromatic which may be substituted by, e.g., halogen, nitro or alkyl groups, or which may be linked by alkylene groups or hetero atoms; saturated or unsaturated aliphatic groups which may be interrupted by hetero atoms, e.g., polyalkylene glycol radicals containing ethylene-, propylene- or butylene-oxide groups (thus the starting compounds may be simple or mixed polyalkylene glycols); and cycloaliphatic radicals which may be partially unsaturated and/or substituted by alkyl or phenyl groups.  In a modification of the process, the organic radical Z may be introduced into the polyglycol simultaneously with or subsequent to the phosphatisation.  An inert liquid may be present and the products may be neutralised with a basic substance.  Many examples are given of starting materials including the condensation products of glycerine +33 moles of ethylene oxide, hexylene glycol +16 ethylene oxide, sorbitol +64 ethylene oxide, o-phthalic acid +20 ethylene oxide, b -naphthylamine +20 ethylene oxide,4,41-diaminodiphenylmethane+40 ethylene oxide, lauric acid amide +24 ethylene oxide, benzoic acid amide +18 ethylene oxide and compounds of the formulae: <FORM:0951445/C2/3> and <FORM:0951445/C2/4>  In Example 5, a condensation product of glycerine with 21 moles of ethylene oxide is refluxed with orthophosphoric acid and the product heated with stearic acid.ALSO:Surface-active polyalkylene glycol derivatives are prepared by reacting a compound of the formula: Z(C2H4O)x. C2H4OH in which Z is an organic radical bound to the C2H4O chain through a "functional" group and x is 1 to 10,000, with from 1/3 to 1 equivalent of phosphorus pentoxide, phosphorus oxychloride, orthophosphoric acid or a polyphosphoric acid formed by dehydrating orthophosphoric acid, at least the final part of the reaction being effected at a temperature above 190 DEG C. while continuously removing volatile by-products, until the reaction product becomes highly viscous and has an acid number between 0 and 4.2.  The products are believed to be tertiary phosphates.  The functional group joining Z to the C2H4O chain is defined as one of the following: an oxygen or sulphur atom, a -COO-, <FORM:0951445/C3/1> , <FORM:0951445/C3/2> , -SO- or -SO2- radical, in which R1 is a hydrogen atom, low alkyl radical or -(CnH2nO)m (C2H4O)xC2H4OH, where m is 0 to 200, x is 1 to 200, m+x not exceeding 200, and n is 3 or 4. The radical Z may be aromatic which may be substituted by, e.g., halogen, nitro or alkyl groups, or which may be linked by alkylene or hetero groups; saturated or unsaturated aliphatic groups which may be interrupted by hetero atoms, e.g. polyalkylene glycol radicals containing ethylene-, propylene- or butylene-oxide groups (thus the starting compounds may be single or mixed polyalkylene glycols); and cycloaliphatic radicals which may be partially unsaturated and/or substituted by alkyl or phenyl groups. In a modification of the process, the organic radical Z may be introduced into the polyglycol simultaneously with or subsequent to the phosphatisation.  An inert liquid may be present.  The products may be neutralized with a basic substance.  Many examples are given of suitable starting materials including monoethers and monoesters of polyglycols, addition products of polyglycols with amines, sulphonamides and carboxylic acid amides and other sulphur and nitrogen containing materials.  In typical illustrative examples: (1) polyethylene glycol (1000) is refluxed with POCl3 in ethylene chloride, the solvent distilled off, stearic acid added and the mixture heated to 240 DEG C. while passing through nitrogen; (2) polyethylene glycol (1000) is heated with oleic acid and ortho-phosphoric acid simultaneously; the phosphoric acid esters of condensation products of octadecandiol with 40 moles ethylene oxide, of p-toluene-sulphonamide with 40 moles ethylene oxide, of stearylamine with 48 moles ethylene oxide and others are similarly prepared (6); (9) a mixture of polyethylene glycol (1000) and a condensate of glycerine with 60 moles of ethylene oxide is partially esterified with POCl3 and then with stearic acid; (11) a copolymer of ethylene oxide (70%) and propylene oxide (30%) of Mol. wt. 4880 is reacted with POCl3; (12) a copolymer of ethylene oxide (60%) and butylene oxide (40%) of Mol. wt. 2912 is reacted with ortho-phosphoric acid.