Patent GB-743254-A (GB)
Title: Lubricating oil compositions
Filed: 1952-11-25
Abstract: Basic sulphurized calcium and barium salts of phenol or nuclear-substituted phenols, having metal contents 10 per cent or more in excess of the amount of metal present in the normal phenates, are prepared by reacting the phenols with the metal oxide or hydroxide and sulphur; alternatively the normal metal phenate may first be formed which is then further treated with the metal oxide or hydroxide and with sulphur.  The process may be carried out in the presence of a glycol as solvent, e.g. ethylene and propylene glycols, butane diol-2,3, pentane diol-2,3 and 2-methyl butane diol-3,4. Substituted phenols referred to are phenols substituted with hydrocarbon radicals, preferably alkyl radicals of 10-18 atoms, e.g. butyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl and triacontyl; and radicals derived from petroleum hydrocarbons such as white oil, paraffin wax and olefin polymers such as polypropylene and polybutylene.  In one example, a mixture of an alkyl phenol having an average of 14-18 carbon atoms in the alkyl group and of 350 molecular weight, calcium hydroxide, sulphur and ethylene glycol was heated at 300 DEG  F. at a pressure of 300 mm. Hg.; the water of reaction and ethylene glycol were distilled off and petroleum lubricating oil added.  The mixture was cooled, a petroleum thinner of boiling range 162-255 DEG  F. added, and the mixture filtered, after which the thinner was removed by heating.  The sulphurized phenate prepared in this way contained 92 per cent more calcium than the normal phenate.  Zinc and calcium salts of mixed aliphatic diesters of dithiophosphoric acids are referred to.  Acids specified are butyl hexyl, methyl hexyl, ethyl hexyl, isopropyl methyl isobutylcarbinyl, butyl methyl isobutyl carbinyl, butyl heptyl, butyl decyl, butyl isoheptyl and butyl octadecyl. In an example a mixed diester is prepared by reacting secondary butyl alcohol, methylisobutylcarbinol and P2S5 at 170 DEG  F. and cooling and filtering the mixture; zinc oxide is then added, the mixture heated at 130 DEG  F. and water of neutralization removed.ALSO:A lubricating oil composition comprises a major proportion of a lubricating oil, a zinc or calcium salt of a mixed aliphatic diester of dithiophosphoric acid and a basic sulphurized calcium and/or barium phenate.  The dithiosphorphoric acid is preferably esterified with one alkyl radical having not more than 4 carbon atoms and another having from 6-18 carbon atoms; examples of suitable radicals are given.  Salts referred to are the zinc and calcium salts of butyl hexyl, methyl hexyl, ethyl hexyl, isopropyl methylisobutylcarbinyl, butyl methylisobutylcarbinyl, butyl heptyl, butyl decyl, butyl isoheptyl and butyl octadecyl dithiophosphoric acids.  The basic sulphurized metal phenates are those having metal contents 10 per cent or more in excess of the amount of metal present in the normal phenates.  The phenates may be derived from phenol itself or phenols having substituents on the benzene ring, e.g. alkyl radicals such as butyl, hexyl, octyl, decyl, dodecyl, hexadecyl, eicosyl and triacontyl; and radicals derived from petroleum hydrocarbons such as white oil, paraffin wax, and olefin polymers such as polypropylene and polybutylene Phenates specified are the calcium and barium salts of octyl, decyl, dodecyl, tetradecyl, hexadecyl and triacontyl phenol. Lubricating oils specified are mineral oils, other hydrocarbon oils, e.g. oils derived from coal products, and synthetic oils. Synthetic oils referred to are alkylene polymers, alkylene oxide polymers, dicarboxylic acid esters, liquid esters of acids of phosphorus and silicon, alkyl benzene polymers and polysiloxanes; examples of such synthetic oils are given.