Patent GB-654968-A (GB)
Title: Improvements in liquid hydrocarbon stabilised against deterioration caused by oxidation or polym erisation
IPC: C10L1/26
Filed: 1948-02-05
Abstract: Oil-soluble ester salts or halogenation products of phosphites resulting from the reaction of phosphorus trichloride with a compound of the class consisting of cyclohexanol, homologues of cyclohexanol, mixtures of cyclohexanol and its homologues and mixtures of homologues of cyclohexanol, are employed as additives in liquid hydrocarbon compositions (see Group III).  The halogenation product may contain a minor amount of combined halogen, present therein either as the result of direct halogenation of the phosphite or as the result of the reaction with the phosphorustrichloride.  The ester salts are obtained by neutralizing free hydroxyl radicles in the phosphite with a base or by partially saponifying the phosphite with a base.  Bases mentioned are sodium, potassium ammonium and substituted ammonium hydroxides, but ester salts of other metals may be obtained from the alkali metal ester salts by double decomposition.  The PCl3-treatment of a commercial cyclohexanol containing minor amounts of homologues such as methyl cyclohexanol is described and it is stated that the treatment yields phosphite esters (RO)3P, (RO)2POH and ROP(OH)2, where R is the radicle of cyclohexanol or its homologue, together with halogen-bearing derivatives of such esters and halides RCl.  The treatment of 3 mols. 4-tert.-amyl-cyclohexanol with 1 mol. PCl3 is also described and the conversion of the phosphite ester thus produced to its calcium salt.ALSO:A liquid hydrocarbon composition, particularly a petroleum lubricating oil or fuel, is stabilized against deterioration from oxidation or polymerization by the inclusion therein of a minor amount of an oil-soluble ester salt or halogenation product of a phosphorus-bearing ester resulting from the reaction of phosphorus trichloride with a compound of the class consisting of cyclohexanol, homologues of cyclohexanol, mixtures of cyclohexanol and its homologues and mixtures of homologue of cyclohexanol.  The halogenation product may contain a minor amount of combined halogen, present therein either as a result of direct halogenation of the phosphorus-bearing ester or as the result of the reaction with the phosphorus trichloride.  The ester salts are obtained by neutralizing free hydroxyl radicles in the phosphorus-bearing ester with a base or by partially saponifying the phosphorus-bearing ester with a base. Bases mentioned are sodium, potassium, ammonium and substituted ammonium hydroxides, but ester salts of other metals may be obtained from the alkali metal ester salts by double decomposition.  The liquid hydrocarbon compositions may contain other addition agents. Thus, in the case of mineral lubricating oil compositions, they may contain extreme pressure addition agents, particularly halogen, phosphorus and/or sulphur compounds, corrosion inhibitors, particularly phosphorus compounds, and pour-point depressors.  In the case of fuels they may contain Diesel fuel dopes, anti-knock compounds such as tetra ethyl lead or iron carbonyl, and anti-oxidants.  In the examples, mineral lubricating oil compositions are described containing (a) PCl3-treated commercial cyclohexanol or (b) calcium salt of PCl3-treated 4-tert.-amyl-cyclohexanol.  The commercial cyclohexanol contained minor amounts of homologues of cyclohexanol such as methyl cyclohexanol; the PCl3-treatment was believed to yield esters of phosphorous acid such as (RO)3P, (RO)2POH and ROP(OH)2, where R is the radicle of cyclohexanol or its homologue, together with halogen-bearing derivatives of such esters and halides RCl.  Further examples describe mineral lubricating oil compositions containing PCl3-treated commercial cyclohexanol and (i) hexachlordiphenyl oxide and o-dichlorbenzene or (ii) hexachlordiphenyl oxide, o-dichlorbenzene, methyl stearate and butyl stearate.  For comparison purposes, mineral lubricating oil compositions containing (i) or (ii) without the PCl3-treated commercial cyclohexanol are described.  Specification 478,338 is referred to.