Patent GB-649976-A (GB)
Title: Polyvalent metal alkoxy phenates and lubricating oils containing them
Filed: 1947-10-24
Abstract: Compounds of the formula [(RO)x.Ar.O.]n.M, where Ar is an aromatic nucleus, R is an aliphatic radical containing not less than 5 carbon atoms, M is a polyvalent metal, n is the valence of M, x is 1 or 2, and both RO. and .O. are directly attached to the aromatic nucleus, are prepared by condensing a di- or tri-hydroxy-aromatic compound with an alcohol, olefine or halide to give a mono- or di-ether still containing a free hydroxy group; the product is either treated with the oxide or hydroxide of the desired metal or converted into an alkali-metal salt and this reacted with a water-soluble salt of the desired metal.  R may be alkyl, alkenyl, cycloalkyl or aralkyl, but is preferably a saturated alkyl radical of 10 to 20 (and most advantageously 12 to 15) carbon atoms, such as decyl, undecyl, lauryl, tetradecyl, cetyl, octadecyl and eicosyl.  It may be a mixture of radicals, e.g. derived from chlorinated kerosene or paraffin wax.  Ar is preferably derived from a dihydroxy benzene, but may have substituents such as alkyl, chloro and nitro groups, and may be derived from pyrogallol or phloroglucinol; it may also be polynuclear, e.g. derived from 1 : 5- or 2 : 7-di-hydroxy-naphthalene.  Mixtures of crude polyhydroxy benzenes or their homologues may be used as starting materials.  M is preferably an alkaline earth metal, but may also be zinc, cadmium, nickel or aluminium.  When etherifying a dihydroxy benzene, the latter is preferably used in excess to minimize formation of the di-ether.  In the examples, cetyl chloride is condensed with the following phenols, and the products converted into their barium salts: resorcinol, hydroquinone, pyrogallol, catechol and p-tert.-butyl catechol.  In the case of pyrogallol, the product is a mixture of the mono- and di-ethers.  Selenium compounds of the formula R1-(Se)m-R2, where R1 and R2 are alkyl, cycloalkyl or aralkyl radicals and m is 1 or 2, may be obtained by reacting an alkyl halide with sodium selenide or an alkyl selenomercaptide, or by oxidation of alkyl selenomercaptans. R1 and R2 are preferably of 7 carbon atoms or more, suitable radicals being specified, and may be derived from chlorinated paraffin wax. Di-"paraffin"-sulphide is obtained by treating chlorinated paraffin wax with sodium sulphide or poly-sulphide.  The Specification as open to inspection under Sect. 91 refers also to the production of basic aluminium salts of the hydroxy-ethers. This subject-matter does not appear in the Specification as accepted.  Reference has been directed by the Comptroller to Specification 639,941, [Group III].ALSO:A lubricant composition comprises a major proportion of a synthetic and/or hydrocarbon lubricating oil and a small amount of p  a phenolic compound of the formula [(RO)x.Ar.O]n.M, where Ar is an aromatic nucleus, R is an aliphatic radical containing not less than 5 carbon atoms, M is a polyvalent metal, n is the valence of M, x is 1 or 2, and both RO. and .O. are directly attached to the aromatic nucleus.  R may be alkyl, alkenyl, cycloalkyl or aralkyl, but is preferably a saturated alkyl radical of 10 to 20 (and most advantageously 12 to 18) carbon atoms, such as decyl, undecyl, lauryl, tetradecyl, cetyl, octadecyl and eicosyl.  It may be a mixture of radicals, e.g. derived from chlorinated kerosene or paraffin wax.  Ar is preferably derived from a dihydroxy benzene, but may have substituents such as alkyl, chloro and nitro groups, and may be derived from pyrogallol or phloroglucinol; it may also be polynuclear, e.g. derived from 1 : 5 or 2 : 7-dihydroxy-naphthalene. M is preferably an alkaline earth metal, but may also be zinc, cadmium, nickel or aluminium.  The additive may be incorporated in amounts ranging from 0.1 to 2.5 per cent, preferably 0.3 to 1.5 per cent, by weight.  Greater proportions may be used, e.g. 10 to 70 per cent, to produce a concentrate suitable for later blending with more oil to yield the finished product.  The oil may be any hydrocarbon oil of lubricating viscosity, e.g. paraffinic, naphthenic or mixed, polyalkenes, synthetic hydrocarbon oils derived from coal and oxides of carbon, or a non-hydrocarbon oil such as alkylene oxide polymers. Preferably, there is used a petroleum oil of 150 to 3000 S.S.U. at 100 DEG  F.  The detergent properties of the additives are improved by the addition of a selenide of the formula R1-(Se)m-R2, where R1 and R2 are alkyl, cycloalkyl or aralkyl radicals, preferably of not less than 7 carbon atoms each, and m is 1 or 2.  Suitable selenides are mentioned.  They may be present in amounts of 0.1 to 2 per cent in the finished oil or 10 to 40 per cent in the concentrate. Corrosion of bearings may be reduced by adding sulphides (e.g. dicetyl sulphide or the sulphides derived from paraffin wax), phosphates (e.g. calcium cetyl phosphate), thiophosphates (e.g. calcium and zinc cetyl thiophosphates, cetylphenyl thiophosphates and methylcyclohexyl thiophosphates) or sulphonates (e.g. calcium mahogany sulphonate) in proportions similar to those of the phenates and selenides.  In examples, the barium salts of the following are used as additives: o-, m- and p-cetoxy-phenols, m-tert.-butyl-o-cetoxy-phenol and a 50-50 mixture of pyrogallol mono- and di-cetyl ethers.  Barium m-cetoxy-phenate is also shown mixed with di-lauryl monoselenide, di-" paraffin " monoselenide, di-benzyl monoselenide and di-octadecyl diselenide.  Specification 537,816 is referred to together with U.S.A.  Specifications 2,360,302 and 2,362,289.  In the Specification as open to inspection under Sect. 91, the use of any metal salt of the alkoxy-phenols is mentioned, sodium, potassium and lithium being specified, and also basic aluminium salts.  This subject-matter does not appear in the Specification as accepted.  Reference has been directed by the Comptroller to Specification 639,941.