Patent GB-677063-A (GB)
Title: Improvements in lubricating compositions stabilised against deterioration by oxidation or polymerisation
IPC: C10M137/10
Filed: 1948-02-05
Abstract: The organic phosphorus-containing component of the reaction product of (a) a trivalent phosphorus- and halogen-containing reagent with (b) an organic hydroxy or mercapto compound, at least one of which reactants contains a cycloaliphatic radicle, is employed as an additive in lubricating compositions (see Group III).  The use of the organic phosphorus-containing component of the reaction product of phosphorus trichloride with cyclohexanol or with the substitution products of cyclohexanol is excluded. The organic phosphorus-containing component of the reaction product of (a) with (b) will include compounds having the structure <FORM:0677063/IV (b)/1> wherein X is oxygen or sulphur, and A, B and C are the same or different radicles selected from the class consisting of hydrogen, metals and organic radicles, at least one of them being a cycloaliphatic radicle.  Instead of the phosphorus-containing component itself, an oil-soluble salt or ester-salt or a halogen-bearing derivative of the phosphorus-containing component may be employed.  The oil-soluble salts or ester-salts may be produced by substituting a metal or basic radicle for one or two of the radicles A, B and C in the structural formula given above. Such a substitution may be effected by partly saponifying the phosphorus-containing component with an aqueous solution of an alkali such as sodium potassium ammonium or substituted ammonium hydroxide.  Similar salts or ester-salts of metals other than the alkali metals may be formed directly by reacting the phosphorus-containing component with the metallic base, or more readily by double decomposition of the alkali salt (or ester-salt) with a salt of the other metal.  A list of suitable metals, whose salts or ester-salts may be employed, is given.  The halogen-bearing derivative of the phosphorus-containing component may contain halogen as the result of the reaction between reactants (a) and (b) or as the result of subsequent direct halogenation of the phosphorus-containing component.  Reactant (a) may have the general formula <FORM:0677063/IV (b)/2> where Y is a halogen, and A1 and B1 are either the same or different halogens or the same or different radicles selected from the class consisting of those having the formulas XR and R where X is oxygen or sulphur and R is an organic radicle or hydrogen.  A list of substances, having this general formula and suitable for use as reactant (a), is given.  A list is also given of substances, having the general formula R1XH where R1 is an organic radicle and X oxygen or sulphur, and which may be employed as reactant (b).  In the examples, (i) phenyl di-(cyclohexyl)-phosphite is prepared by reacting 1 mol. of phenyl-dichlorophosphite with 2 mols. of cyclohexanol; (ii) the calcium salt of cyclohexyl p-di-isobutyl-phenyl phosphite is prepared by reacting 1 mol. of p-di-isobutylphenyl dichlorophosphite with 1 mol. of cyclohexanol and converting the reaction product to its calcium salt; (iii) 2-ethyl-cyclohexyl dicetyl phosphite is prepared by reacting 1 mol. of dicetyl chlorophosphite with 1 mol. of 2-ethyl-cyclohexanol, and (iv) cyclohexyl di-n-butyl trithiophosphite is prepared by reacting 1 mol. of di-n-butyl-chloro-dithiophosphite with 1 mol. of cyclohexyl mercaptan.  Specification 478,338, [Group III], is referred to.  The Specification as open to inspection under Sect. 91, includes a list of organic radicles which may be employed as radicles A, B and C in the structural formula given above.  This subject-matter does not appear in the Specification as accepted.ALSO:A lubricating oil composition is stabilized against deterioration by oxidation or polymerization by the presence therein of the organic phosphorus-containing component of the reaction product of (a) a trivalent phosphorus-and halogen-contain-reagent with (b) an organic hydroxy or mercapto compound, at least one of which reactants contains a cycloaliphatic radicle.  The use of the organic phosphorus-containing component of the reaction product of phosphorus trichloride with cyclohexanol or with the substitution products of cyclohexanol is excluded.  The lubricating oil may be of petroleum, animal, vegetable or marine origin.  The organic phosphorus-containing component of the reaction product of (a) with (b) will include compounds having the structure <FORM:0677063/III/1> wherein X is oxygen or sulphur, and A, B and C are the same or different radicles selected from the class consisting of hydrogen, metals and organic radicles, at least one of them being a cycloaliphatic radicle.  Instead of the phosphorus-containing component itself, an oil soluble salt or ester-salt or a halogen-bearing derivative of the phosphorus-containing component may be employed as the stabilizer in the lubricating oil composition. The oil-soluble salts or ester-salts may be produced by substituting a metal or basic radicle for one or two of the radicles A, B and C in the structural formula given above.  Such a substitution may be affected by partly saponifying the phosphorus-containing component with an aqueous solution of an alkali such as sodium, potassium, ammonium or substituted ammonium hydroxide.  Similar salts and ester-salts of metals other than the alkali metals may be formed directly by reacting the phosphorus-containing component with the metallic base, or more readily by double decomposition of the alkali salt (or ester-salt), with a salt of the other metal.  A list of suitable metals, whose salts or ester-salts may be employed, is given.  The halogen bearing derivative of the phosphorus-containing component may contain halogen as the result of the reaction between reactants (a) and (b) or as the result of subsequent direct halogenation of the phosphorus-containing component.  Reactant (a) may have the general formula <FORM:0677063/III/2> where Y is a halogen, and A1 and B1 are either the same or different halogens or the same or different radicles selected from the class consisting of those having the formulas XR and R where X is oxygen or sulphur and R is an organic radicle or hydrogen.  A list of substances, having this general formula and suitable for use as reactant (a), is given.  A list is also given of substances having the general formula R1XH where R1 is an organic radicle and X is oxygen or sulphur, and which may be employed as reactant (b).  The lubricating oil composition may contain additional ingredients such as detergents, particularly salts of petroleum sulphonic acids, and extreme pressure addition agents. In the examples, mineral lubricating oil compositions are described containing (i) phenyldi-(cyclohexyl) phosphite (prepared by reacting 1 mol. of phenyldichloro phosphite with 2 mols. of cyclohexanol), (ii) the calcium salt of cyclohexyl p-di-isobutyl-phenyl phosphite (prepared by reacting 1 mol. of p-di-isobutyl-phenyl dichloro phosphite with 1 mol. of cyclohexanol and converting the reaction product to its calcium salt) (iii) 2-ethyl-cyclohexyl di-cetyl phosphite (prepared by reacting 1 mol. of dicetyl chlorophosphite with 1 mol. of 2-ethyl-chlorophosphite with 1 mol. of 2-ethyl-cyclohexanol) or (iv) cyclohexyl di-n-butyl trithiophosphite (prepared by reacting 1 mol. of di-n-butyl-chloro-dithio phosphite with 1 mol. of cyclohexyl mercaptan).  Specification 478,338 is referred to.  The Specification as open to inspection under Sect. 91 refers to the use of the stabilizers as corrosion inhibitors when added to engine fuels such as gasoline and includes a list of organic radicles which may be employed as radicles A, B and C in the structural formula given above.  This subject-matter does not appear in the Specification as accepted.