Patent GB-736448-A (GB)
Title: Process of producing tertiary phosphoric acid esters of partial carboxylic acid esters of polyhydric alcohols
IPC: C07F9/09
Filed: 1953-04-22
Abstract: Previously formed tertiary phosphoric esters, still capable of esterification, of polyhydric alcohols or polyhydric ether alcohols are further esterified with polybasic carboxylic acids with simultaneous polycondensation (see Group IV (b)).  Specified acids include phthalic, adipic, succinic, tartaric, diglycollic and maleic acids.  In another embodiment of the invention tertiary polycondensed phosphoric esters which still contain free hydroxyl groups are further esterified with carboxylic acids.  The products obtained vary from an oily consistency to that of soft resins.  By esterification with mixtures of acids, for example a mixture of stearic and succinic acids, it is possible to obtain surface active compounds of high molecular weight.  The compounds are used as dispersing agents, detergents, sizing agents, for degreasing and rust prevention and as emulsifiers.  In examples, (3) the ester obtained by reaction of the phosphoric acid ester dichloride of octadecyl diethylene glycol ether (1 mol.) and triethylene glycol (2 mols.) is reacted with succinic acid, (4), the tertiary polycondensed polyglycol phosphate obtained by reaction of phosphorus oxychloride (1 mol.) and triethylene glycol (2 mols.) is reacted with abietic acid, (5) the ester from polypropylene glycol (3 mols.) and phosphorus oxychloride (1 mol.) is reacted with a mixture of stearic acid and succinic anhydride. Specification 706,410 is referred to.ALSO:Previously formed tertiary phosphoric esters, still capable of esterification, of polyhydric alcohols or polyhydric ether alcohols are further esterified with one or more carboxylic acids or their anhydrides.  Mixed tertiary phosphoric esters having monohydric alcohol or phenol radicals as well as at least one polyhydric alcohol radical, and suitable polycondensed tertiary phosphoric esters, are also further esterified.  Specified polyhydric alcohols and ether alcohols include glycols, glycerol, hexitol, anhydrohexitol pentaerythritol, polyethylene glycols (mol. wt. 150 to 2000), polyglycerol and polyoxalkylpentaerythritol.  Specified monohydric alcohol or phenol radicals include monobutyl glycol ether, naphthyl-propylene glycol ether, naphthol, cyclohexanol and oxyethylmorpholin.  The acids specified include stearic, ricinoleic, benzoic, phthalic, tartaric, diglycollic, g -ketopimelic, maleic, abietic and phenoxyacetic acids. When dicarboxylic acids are used simultaneous polycondensation occurs (see Group IV (a)).  The reaction is carried out by heating the said esters with the carboxylic acid or anhydride at above 100 DEG  C. and removing the water formed.  In examples (1) the ester from polyethylene glycol (3 mols.) and phosphorus oxychloride (1 mol.) is reacted with stearic acid; (2) the ester from polyethylene glycol (1 mol.) and phosphorus oxychloride (0.33 mol.) is reacted with a mixture of stearic and oleic acids; (3) the ester obtained by reaction of the phosphoric acid ester dichloride of octadecyl diethylene glycol ether (1 mol) and triethylene glycol (2 mols.) is further reacted with succinic acid; (4) the tertiary polycondensed polyglycol phosphate obtained by reaction of phosphorus oxychloride (1 mol.) and triethylene glycol (2 mols.) is reacted with abietic acid; (5) the ester from polypropylene glycol (3 mols.) and phosphorus oxychloride (1 mol.) is reacted with a mixture of stearic acid and succinic acid anhydride; (6) the ester formed by reaction of para-octylphenol (1 mol.) with phosphorus oxychloride (1 mol.) followed by reaction with polyethylene glycol (2 mols.), is further esterified with stearic acid; (7) the ester from a mixture of polyethylene glycols (3 mols.) and phosphorus oxychloride (1 mol.) is reacted with lauric acid; (8) the ester formed by reaction of para-octylphenyl diglycol ether (2 mols.) with phosphorus oxychloride (1 mol.) followed by reaction with polyethylene glycol (1 mol.) is further esterified with lauric acid.  The products have surface active properties and may be used as dispersing, detergent, antistatic and sizing agents, for rust preventing and degreasing, and as emulsifiers for ointments and foodstuffs.  Specification 706,410, [Group IV (a)], is referred to.