Phosphorus compounds of the blue of molybdenum which are soluble in organic liquids, and their use as additives for lubricating

摘要

The invention comprises complexes of molybdenum blue with phosphorus compounds of the formula: FORM:0844811/IV(b)/1 where X is oxygen or sulphur; R is hydrogen, an aliphatic group containing at least 4 carbon atoms, a halogen-substituted aliphatic group containing at least 4 carbon atoms, an alkylthioalkyl group (ASAlk, where Alk contains at least 4 carbon atoms), an aryl group, or halogen- or alkyl-substituted aryl group, an arylthioaryl group, or a polyoxyethylene monoether residue; and Y is a group of formula OR1, NHR11 or NR112, where R1 is a radical of the same type as R (other than hydrogen), and R11 is an alkyl radical containing at least 2 carbon atoms. The complexes may be prepared by reacting the phosphorus compound with a partially reduced aqueous solution of molybdic acid at a temperature up to the boiling point of the reaction mixture, e.g. in the presence of an inert organic solvent; the partially reduced molybdic acid solution must not become blue except in the presence of the phosphorus compound. The partially reduced molybdic acid solution may be prepared in situ by the use of an acidic nonreduced dilute aqueous solution of a molybdate and a reducing metal such as aluminium. Formulae are given of various preferred types of phosphorus compound. The complexes are used in lubricating compositions (see Group III). Preparations of the phosphorus compounds and intermediates-Dialkyl thiophosphates can be prepared by transesterification, e.g. by reacting diethyl phosphite with a higher alcohol and treating the dialkyl phosphite with sulphur; this may be used to prepare dicetyl, dilauryl and dioleyl thiophosphates. Monoaryl phosphates can be prepared by hydrolysis of an aryl dichlorophosphate. Amidophosphoric acid esters can be prepared by reacting a phosphorus dialkylamido-oxydichloride (obtained from POCl3 and a secondary amine) with a suitable alcohol or phenol or sodium derivative thereof.ALSO:A lubricating composition consisting of a lubricant in admixture with a complex of molybdenum blue with a phosphorus compound of the formula: FORM:0844811/III/1 where X is oxygen or sulphur; R is hydrogen, an aliphatic group containing at least 4 carbon atoms, a halogen-substituted aliphatic group containing at least 4 carbon atoms, an alkylthioalkyl group (ASAlk, where Alk contains at least 4 carbon atoms), an aryl group, a halogen- or alkyl-substituted aryl group, an arylthioaryl group, or a polyoxyethylene monoether residue; and Y is a group of formula OR1, NHR11 or NR112, where R1h is a radical of the same type as R (other than hydrogen), and R11 is an alkyl radical containing at least 2 carbon atoms. The compositions may also contain the free phosphorus compound. Suitable lubricants are mineral and synthetic hydrocarbon oils, animal and vegetable oils, castor oil, and synthetic oils such as tricresyl phosphate and polyethylene glycols. A specific composition used for testing lubricant properties consisted of SAE 30 oil containing 3% chlorinated paraffin, 1.5% dibenzyl glycol xanthate, and 1% of the molybdenum blue/diethylamido-dodecylphosphate complex. Partially reduced molybdic acid solutions (not reduced to molybdenum blue) are obtained by reduction of an acid solution of a molybdate or molybdic acid with a reducing metal such as aluminium. A solution having the degree of oxidation Mo2O5.3MoO3 is so obtained; a similar solution is prepared by mixing in suitable proportions a solution containing MoVI and a solution containing MoV (prepared by reduction with Al of a MoVI solution). A solution containing MoIV is prepared by aluminium reduction of an acid MoVI solution.